14-substituted marcfortines and derivatives useful as antiparasitic agents

ABSTRACT

There are disclosed 14 alpha -hydroxymarcfortine derivatives of the natural products marcfortine A, B, C, and D useful in the treatment and prevention of helminth and arthropod infections of animals and plants. The synthetic derivatives are of Formula (I).

CROSS-REFERENCE

This application is a 371 of PCT/US94/06037 filed Jun. 7, 1994.

BACKGROUND OF THE INVENTION

The marcfortines are known compounds and are disclosed by Polonsky etal. in Journal of the Chemical Society Chemical Communications 1980601-602 (Marcfortine A) and Tetrahedron Letters 1981 22 1977-1980(Marcfortines B and C). The compounds are fungal metabolites ofPenicillium roqueforti. The marcfortines are structurally related to theparaherquamides which are also known compounds. The paraherquamides aredisclosed by Yamazaki et al. in Tetrahedron Letters 1981 22 135-136, andby Blanchflower et al., Journal of Antibiotics, 1991, 44, 492-497. U.S.Pat. Nos. 4,866,060 and 4,923,867 disclose the use of the marcfortinesA, B, and C, and certain derivatives thereof as useful for the treatmentand prevention of parasitic diseases in animals.

WO 92/22555 (published 23 Dec. 1992) generically discribes a marcfortineor paraherquamide derivative (i.e. partial formula (III) substituted atposition 14 with methyl or methyl and hydroxy, however no description ofhow to prepare such 14-methyl-14-hydroxymarcfortine compounds isprovided.

Paraherquamide has the following structure: ##STR2##

Marcfortine A has the following structure: ##STR3##

Marcfortine B has the following structure: ##STR4##

Marcfortine C has the following structure: ##STR5##

Marcfortine D has the following structure: ##STR6##

WO 91/09961 (published 11 Jul. 1991) discloses various derivatives ofmarcfortine and paraherquamide, and 12a-N-oxides thereof, as well as theproduction the production of VM 29919 (paraherquamide) and VM 55596 (the12a-N-oxide of paraherquarnide) inter alia from Penicillium Sp. IMI332995.

U.S. Pat. No. 4,873,247 discloses derivatives of paraherquamide and astrain of Penicillium charlessi MF 5123 (ATCC 20841) for the productionof paraherquamide. U.S. Pat. No. 4,978,656 (as well as EP 390532-A,EP-301742-A) discloses various synthetic derivatives of paraherquamideas well as the production of paraherquamide from Penicillium charlessiMF 5123 (ATCC 20841).

SmithKline Beecham in International Publication No. WO 92/22555(published 23 Dec. 1992) generically discloses 14α-hydroxy-marcfortinecompounds and a process which uses the 14-hydroxy-14-methylmarcfortinecompounds for the production of antiparasitic drugs. However, noenabling description of any means of preparation of14α-hydroxy-marcfortine or 14α-hydroxy-14β-methyl-marcfortine compoundsis provided.

SUMMARY OF THE INVENTION

This invention is concerned with the synthesis of 14-substitutedmarcfortines A, B, C, and D and derivatives thereof and the use of thesecompounds as antiparasitic agents. Thus it is an object of thisinvention to describe these marcfortine derivatives. A further object ofthis invention is to describe processes for the preparation of thesecompounds. A still further object is to describe the use of the instantcompounds as antiparasitic agents in the treatment and prevention ofparasitic diseases. A still further object is to describe compositionsfor the treatment of parasitic diseases which contain the novelcompounds of this invention as the active ingredient thereof. Furtherobjects will become apparent from a reading of the followingdescription.

DESCRIPTION OF THE INVENTON

The compounds of the instant invention are represented by Formula I:##STR7## wherein:

m is 0 or 1;

Z is O or S;

Y is an oxygen atom (--O--) or a bond;

R₁ is hydrogen, C₁ -C₇ alkyl, cyclo C₃ -C₈ alkyl, benzyl, C₂ -C₇alkanoyl (--C(O)C₂ -C₇ alkyl) {optionally substituted with carboxy(--COOH), C₁ -C₇ alkanoyl, carboC₁ -C₇ alkoxy (--C(O)OC₁ -C₇ alkyl),--NR₄ R₅, aminocarbonyl (--C(O)NR₄ R₅)}, C₁₀ -C₂₄ alkanoyl (--C(O)C₁₀-C₂₄ alkyl, cyclo C₃ -C₈ alkanoyl {optionally substituted with carboxy,C₁ -C₇ alkanoyl, carboC₁ -C₇ alkoxy, --NR₄ R₅, aminocarbonyl},alkanoyloxymethylene (--CH₂ OC(O)--C₂ -C₇ alkyl), benzoyloxymethlene(--CH₂ OCO(O)phenyl) {optionally substituted with 1 or 2 groups selectedfrom halogen, C₁ -C₄ alkyl, haloC₁ -C₇ alkyl, nitro, cyano and C₁ -C₇alkoxy}. C₁₀ -C₂₄ alkenoyl (--C(O)C₉ -C₂₃ alkenyl), benzenesulfonyl(--SO₂ CH₂ phenyl) {optionally substituted with 1 or 2 groups selectedfrom halogen, C₁ -C₄ alkyl, haloC₁ -C₇ alkyl, nitro, cyano and C₁ -C₇alkoxy}, C₁ -C₄ alkylaminocarbonyl (--C(O)N(C₁ -C₄ alkyl)₂), C₁ -C₄alkylaminothiocarbonyl (--C(S)N(C₁ -C₄ alkyl)₂), C₁ -C₇ alkoxycarbonyl,phenoxycarbonyl {optionally substituted with 1 or 2 groups selected fromhalogen, C₁ -C₄ alkyl, haloC₁ -C₇ alkyl, nitro, cyano and C₁ -C₇alkoxy}, --C(O)NR'₄ R'₅, --P(=X)(R₂)(R₃), --SR₆, --SO₂ NR₄ R5, benzoylsubstituted at the 3 or 4 position with --CH₂ NR₄ R₅ or bicycloC₈ -C₁₂alkanoyl;

R₄ and R₅, being the same or different, are selected from hydrogen, C₁-C₇ alkyl, phenyl {optionally substituted with 1 or 2 groups selectedfrom halogen, C₁ -C₄ alkyl, haloC₁ -C₇ alkyl, nitro, cyano and C₁ -C₇alkoxy} or when taken together with N, form a saturated or unsaturatedheterocyclic amine ring;

R'₄ and R'₅, being the same or different, are selected from C₁ -C₇alkyl, cyclo(C₃ -C₈)alkyl, phenyl {optionally substituted with 1 or 2groups selected from halogen, C₁ -C₄ alkyl, haloC₁ -C₇ alkyl, nitro,cyano and C₁ -C₇ alkoxy} or when taken together with N, form a saturatedheterocyclic amiine ring optionally containing 1 or 2 additionalheteroatoms selected from N, O or S;

X is O or S;

R₂ and R₃, being the same or different, are selected from C₁ -C₇ alkyl,phenyl {optionally substituted with 1 or 2 groups selected from halogen,C₁₋₄ alkyl, haloC₁ -C₇ alkyl, nitro, cyano and C₁ -C₇ alkoxy}, C₁ -C₇alkoxy, thio(C₁ -C₇)alkoxy, phenoxy, thophenoxy, --NR₇ R₈ {where R₇ andR₈, being the same or different, are selected from H, C₁ -C₇ alkyl ortaken together with N, form a saturated heterocyclic ring}, or takentogether with P form a 4- to 7-membered heterocyclic ring;

R₆ is C₁ -C₇, alkyl, haloC₁ -C₇ alkyl, carboC₁ -C₇ alkoxy, --NR₉ R₁₀where R₉ and R₁₀, being the same or different, are C₁ -C₇ alkyl orphenyl (optionally substituted with 1 or 2 groups selected from halo,lower alkyl, haloC₁ -C₇ alkyl, nitro, cyano, C₁ -C₇ alkoxy);

R₂₄ is hydrogen, halogen or C₁ -C₇ alkoxy;

R₂₅ is hydrogen or halogen;

R_(18a) is hydrogen, C₁ -C₇ alkyl, C₂ -C₈ alkoxyalkyl, C₂ -C₈ alkenyl,C₂ -C₈ alkynyl or benzyl;

R_(14a) is hydroxyl, hydrogen, C₁ -C₇ alkyl, C₂ -C₈ alkoxyalkyl,cyclo(C₃ -C₈)alkyl or benzyl (optionally substituted with 1 or 2 groupsselected from halo, lower alkyl, haloC₁ -C₇ alkyl, nitro, cyano, C₁ -C₇alkoxy);

R_(14b) is hydrogen, hydroxyl, C₁ -C₇ alkoxy, cyclo(C₃ -C₈)alkyl orbenzoxyl (optionally substituted with 1 or 2 groups selected from halo,lower alkyl, haloC₁ -C₇ alkyl, nitro, cyano, C₁ -C₇ alkoxy);

R_(15a) and R_(15b) are both hydrogen, with the provisio that when oneof R_(14a) or R_(14b) is hydroxyl and the other is hydrogen or methyl,R_(15a) and R_(15b) can be hydrogen or methyl;

the broken line between carbons 24 and 25 represents a single or doublebond; and with the overall proviso that R_(14a) and R_(14b) are not bothhydrogen.

The compounds of this invention include pharmaceutically acceptablesalts thereof as well as 12a-N-oxides thereof.

Another aspect of this invention provides 14-substituted marcfortine A,and B compounds of Formula IA: ##STR8##

Another aspect of this invention provides 14-substituted thiomarcfortineA, and B compounds of Formula IB: ##STR9##

Another aspect of this invention provides an 14-substituted marcfortineC and D compounds of Formula II: ##STR10##

Another aspect of this invention provides an 14-substitutedthiomarcfortine C and D compounds of Formula III: ##STR11##

The carbon content of various hydrocarbon containing moieties isindicated by a prefix designating the minimum and maximum numer ofcarbon atoms in the moiety, i.e., the prefix C_(i) -C_(j) indicates acarbon atoms content of the integer "i" to the integer "j" carbon atoms,inclusive. Thus, C₁ -C₃ alkyl refers to alkyl of 1-3 carbon atoms,inclusive, or methyl, ethyl, propyl, and isopropyl.

With respect to the above, "C₁ -C₇ alkyl" is intended to include thosealkyl groups of from 1 to 7 carbon atoms in either a straight orbranched chain. Examples of such lower alkyl groups are methyl, ethyl,propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyland the like.

Cyclo(C₃ -C₈)alkyl is intended to include alkyl rings of 3 to 8 members.Examples of cyclo(C₃ -C₈)alkyl groups are cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, bicyclo 2.2.1!heptyl, and thelike.

C₁ -C₈ alkoxy is intended to include those alkoxy groups of from 1 to 8carbon atoms in either a straight or branched chain. Examples of such C₁-C₈ alkoxy groups are methoxy, ethoxy, propoxy, isopropoxy, butoxy,sec-butoxy, pentoxy, hexoxy, heptoxy, and the like.

C₂ -C₇ alkanoyl is intended to include those alkanoyl groups of from 2to 7 carbon atoms in either a straight or branched chain. Examples ofsuch C₂ -C₇ alkanoyl groups include acetyl, propionyl, isopropionyl,butyryl, pentanoyl, hexanoyl and the like.

C₁₀ -C₂₄ alkanoyl (--C(O)C₉ -C₂₃ alkyl) is intended to include thosealkanoyl groups of from 10 to 24 carbon atoms in either a straight orbranched chain. Examples of such C₁₀ -C₂₄ alkanoyl groups includedecanoyl --C(O)(CH₂)₉ CH₃ !, lauroyl --C(O)(CH₂)₁₀ CH₃ !, tridecanoyl--C(O)(CH₂)₁₁ CH₃ !, myristoyl --C(O)(CH₂)₁₂ CH₃ !, pentadecanoyl--C(O)(CH₂)₁₃ CH₃ !, palmitoyl --C(O)(CH₂)₁₄ CH₃ !, magaroyl--C(O)(CH₂)₁₅ CH₃ !, stearoyl --C(O)(CH₂)₁₆ CH₃ !, arachidoyl--C(O)(CH₂)₁₈ CH₃ !, heneicoisanoyl --C(O)(CH₂)₁₉ CH₃ !, behenoyl--C(O)(CH₂)₂₀ CH₃ !, tricosanoyl --C(O)(CH₂)₂₁ CH₃ !, tetracosanoyl--C(O)(CH₂)₂₂ CH₃ !, and the like.

C₁₀ -C₂₄ alkenoyl (--C(O)C₉ -C₂₃ alkenyl) is intended to include thoseunsaturated groups of from 10 to 24 carbon atoms in either a straight orbranched chain. Examples of such C₁₀ -C₂₄ alkenoyl groups includeundecylenoyl --C(O)(CH₂)₇ CH:CHCH₃ !, oleoyl --C(O)(CH₂)₇ CH:CH(CH₂)₇CH₃ !, linoloyl --C(O)(CH₂)₇ CH:CH.CH₂.CH:CH(CH₂)₄ CH₃ !, and the like.

The term "C₂ -C₈ alkoxyalkyl" is intended to include those lower alkoxysubstituted lower alkyl groups containing from 2 to 8 carbon atoms andfrom 1 to 3 oxygen atoms in either a straight or branched chain.Examples of such C₂ -C₈ alkoxyalkyl groups include methoxymethyl,methoxyethoxymethyl, methoxyethoxyethoxymethyl, ethoxyethyl, and thelike. Examples of C₁ -C₈ alkoxymethyl are methoxymethyl, ethoxymethyl,propoxymethyl, butoxymethyl, pentoxymethyl, butoxymethyl, pentoxymethyl,hexoxymethyl, and heptoxymethyl, and isomeric forms thereof.

The term alkanoyloxymethylene is intended to include those alkanoyloxysubstituted methylenes containing from 2 to 8 carbon atoms in either astraight or branched chain. Examples of such C₂ -C₈ alkanoyloxymethylenegroups include acetoxymethyl, tert-butoxymethyl, n-propoxymethyl,valeroxymethyl and the like.

The term "substituted benzoyloxymethylene" is intended to include thosebenzoyloxymethyl groups in which the benzene ring is substituted withfrom 0 to 3 substituents selected from lower alkyl, trifluoromethyl, C₁-C₇ alkoxy, nitro, or cyano groups, and halogen atoms.

The term "substituted benzenesulfonyl" is intended to include thosebenzenesulfonyl groups in which the benzene ring is substituted withfrom 0 to 3 substituents selected from lower alkyl, trifluoromethyl, C₁-C₇ alkoxy, nitro, or cyano groups, and halogen atoms.

The term "halogen" is intended to include the halogen atoms fluorine,chlorine, bromine and iodine.

The term "halo C₁ -C₇ alkyl" is intended to include those halogensubstituted C₁ -C₇ alkyl groups containing from 1 to 7 carbon atoms ineither a straight or branched chain and from 1 to 3 halogen atoms.Examples of haloC₁ -C₇ alkyl include fluoromethyl, 2-bromoethyl,3-chloropropyl, 5-iodopentyl, trifluoromethyl, and the like.

The term "C₂ -C₈ alkenyl" is intended to include those lower alkylgroups containing from 2 to 8 carbon atoms in either a straight orbranched chain which contains 1 to 2 carbon-carbon double bonds.Examples of such C₂ -C₈ alkenyl groups include allyl, 3-butenyl,2,4-pentadienyl, hexenyl, and the like.

The term "C₂ -C₈ alkynyl" is intended to include those alkynyl groupscontaining from 1 to 8 carbon atoms in either a straight or branchedchain which contains 1 to 2 carbon-carbon triple bonds. Examples of suchC₂ -C₈ alkynyl groups include propargyl, 2-butynyl, 2,4-pentadiynyl,5-hexynyl, and the like.

Examples of "alkoxycarbonyl" (--C(═O)O--(CH₂)_(p) --C₁ -C₇ alkoxy)include ethoxycarbonyl, isopropoxycarbonyl, methoxycarbonyl,butoxycarbonyl, hexoxycarbonyl and the like. C₁ -C₇ alkanoyl is intendedto include alkyl groups of from 1 to 7 carbon atoms in either a straightor branched chain. Examples of C₁ -C₇ alkanoyl include acetyl,propionyl, iso-butyryl, valeryl, 5-methylhexanoyl, and the like.

Examples of aminocarbonyl (--C(═O)NR₄ R₅) include dimethylaminocarbonyl,propylmethylaminocarbonyl, dibutylaminocarbonyl, isopropylaminocarbonyl,hexylaminocarbonyl and the like.

Examples of aminothiocarbnyl (--C(═S)NR₄ R₅) includedimethylaminothiocarbonyl, propylmethylaminothiocarbonyl,dibutylaminothiocarbonyl, isopentylaminothiocarbonyl,hexylaminothiocarbonyl and the like.

Examples of the group --P(═X)(R₂)(R₃) include diethyl thiophosphoryl,phenylmethoxyphosphonyl, 2-thioxo-1,3,2-dioxaphosphorinanyl,N,N-dimethylmethoxyphosphoramidyl, diphenylphosphinyl and the like.

Examples of --SR₆ include 2,4-dinitrobenzenesulfenyl,dimethylaminosulfenyl, ethoxycarbonylsulfenyl, trichloromethylsulfenyl,4-morpholinosulfenyl and the like.

Examples of --SO₂ NR₄ R₅ include dimethylsulfamoyl,phenylmethylsulfamoyl, 4-morpholinosulfamoyl, piperidinylsulfamoyl andthe like.

The term "P containing heterocyclic ring" is intended to include1,3-dioxa-2-phosphorinane, 1-aza-3-oxa-2-phospholane,1,3-diaza-2-phospholane, 1-thia-3-oxa-2-phospholane, and the like.

Examples of heterocyclic amine rings according to --NR₄ R₅, --NR'₄ R'₅and --NR₇ R₈ are:

4-morpholine,

4-phenyl-1-piperazine,

4-(2-pyridinyl)-1-piperazine,

2,6-dimethyl-4-morpholine,

1-pyrrolidine,

4-methyl-1-piperazine,

1-piperidine,

4-phenyl-1-piperidine

thiazolidine,

4-phenyl-1,2,3,6-tetrahydropyridine,

4-phenylpiperidine,

ethyl prolinate,

tetrahydrofurylamine,

3-pyrroline,

thiazolidine-4-carboxylic acid,

thiomorpholine,

nipecotamide,

2-methylpiperidine,

3-methylpiperidine,

4-methylpiperidine,

N-methylpiperazine,

1-methylhomopiperazine,

1-acetylpiperazine,

N-carboethoxypiperazine,

Pharmaceutically acceptable salts means salts useful for administeringthe compounds of this invention and include mesylate, hydrochloride,hydrobromide, hydroiodide, sulfate, phosphate, acetate, propionate,lactate, maleate, malate, succinate, tartrate, and the like. These saltsmay be in hydrated form.

Preferred compounds of this invention are compounds of Formula IA and IBare compounds where R_(14a) is hydroxyl and hydrogen, R_(14b) ishydrogen, methyl, and ethyl; R₂₄ and R₂₅ are hydrogen; R_(18a) ishydrogen, C₁ -C₄ alkyl, C₂ -C₄ alkoxyalkyl, C₂ -C₄ alkenyl or benzyl;and the broken line between carbons 24 and 25 represents a double bond.

Examples of the preferred compounds of this invention are as follows:

14β-methylmarcfortine A,

14β-ethylmarcfortine A, and

14α-hydroxy-14β-ethylmarcfortine A; more preferably

14α-hydroxy-14β-methylmarcfortine A;

14α-hydroxy-14β-methyl-15α-methylmarcfortine A; and most preferably

14α-hydroxymarcfortine A and

14α-hydroxy-15α-methylmarcfortine A.

The following compounds can be prepared from 14α-hydroxymarcfortines,14α-hydroxy-14β-methylmarcfortines, 14β-methylmarcfortines,14β-ethylmarcfortines, or 14α-hydroxy-14β-ethylmarcfortines,14α-hydroxy-14β-methyl-15α-methylmarcfortines, and14α-hydroxy-15α-methylmarcfortines by employing procedures described inEP 0 354 615 A1 (published 14 Feb 90), and PCT/US92/09483 (WO 93/10120,published 27 May 93), both of which are incorporated herein byreference:

1-acetoxymethyl-14α-hydroxymarcfortine A;

1-diethoxyphosphoryl-14α-hydroxymarcfortine A;

1-dimethylsulfamoyl-14α-hydroxymarcfortine A;

1-cyclopropylcarbonyl-14α-hydroxymarcfortine A;

2-bicyclo 2.2.1!heptanoyl-14α-hydroxymarcfortine A;

1(1-piperidinyl)thiocarbonyl-14α-hydroxymarcfortine A;

1-succinoyl-14α-hydroxymarcfortine A;

1(4-morpholinosulfenyl)-14α-hydroxymarcfortine A;

1(2,4-dinitrobenzenesulfenyl)-14α-hydroxymarcfortine A;

24-propoxy-24,25-dihydro-14α-hydroxymarcfortine A;

1(p-toluenesulfonyl)-14α-hydroxymarcfortine A;

1-acetyl-14α-hydroxymarcfortine A;

1-methyl-14α-hydroxymarcfortine A;

1-benzyl-14α-hydroxymarcfortine A;

1-dimethylcarbamoyl-14α-hydroxymarcfortine A;

1-methoxycarbonyl-14α-hydroxymarcfortine A;

14α-hydroxymarcfortine B;

24,25-dihydro-14α-hydroxymarcfortine B;

24-methoxy-24,25-dihydro-14α-hydroxymarcfortine B;

1-(p-toluenesulfonyl)-14α-hydroxymarcfortine B;

1-ethyl-14α-hydroxymarcfortine B;

1-benzyl-14α-hydroxymarcfortine B;

18a-ethyl-14α-hydroxymarcfortine B;

18a-benzyl-14α-hydroxymarcfortine B;

18a-methoxyethoxymethyl-14α-hydroxymarcfortine B;

18a-allyl-14α-hydroxymarcfortine B;

18a-propargyl-14α-hydroxymarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxymarcfortine B;

1,18a-bis-ethyl-14α-hydroxymarcfortine B;

1,18a-bis-benzyl-14α-hydroxymarcfortine B;

18a-ethyl-24-methoxy-14α-hydroxymarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxymarcfortine B;

18a-ethyl-24,25 dihydro-14α-hydroxymarcfortine B;

24,25 dihydro-14α-hydroxymarcfortine C;

1-(p-bromobenzene sulfonyl)-14α-hydroxymarcfortine C;

1-propionyl-14α-hydroxymarcfortine C;

1-propyl-14α-hydroxymarcfortine C;

1-benzyl-14α-hydroxymarcfortine C;

18a-propyl-14α-hydroxymarcfortine C;

18a-benzyl-14α-hydroxymarcfortine C;

18a-methoxyethoxymethyl-14α-hydroxymarcfortine C;

18-allyl-14α-hydroxymarcfortine C;

18a-propargyl-14α-hydroxymarcfortine C;

1,18a-bis-propyl-14α-hydroxymarcfortine C;

1,18a-bis-benzyl-14α-hydroxymarcfortine C;

14α-hydroxymarcfortine C;

b 1-(4-carbethoxy-1,3-thiazolidinin-3-yl)carbonyl-14α-hydroxymarcfortineA;

1-palmitoyl-14α-hydroxymarcfortine A;

1-(4-morpholinocarbonyl)14α-hydroxymarcfortine A;

1-palmitoyl-14α-hydroxymarcfortine D;

1-(4-morpholinocarbonyl)-14α-hydroxymarcfortine D;

14α-hydroxymarcfortine D;

1-acetoxymethyl-14α-hydroxymarcfortine D;

1-diethoxyphosphoryl-14α-hydroxymarcfortine D;

1-dimethylsulfamoyl-14α-hydroxymarcfortine D;

1-cyclopropylcarbonyl-14α-hydroxymarcfortine D;

2-bicyclo 2.2.1!heptanoyl-14α-hydroxymarcfortine D;

1-(1-piperidinyl)thiocarbonyl-14α-hydroxymarcfortine D;

1-succinoyl-14α-hydroxymarcfortine D;

1-(4-morpholinosulfenyl)-14α-hydroxymarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxymarcfortine D;

24-propoxy-24,25-dihydro-14α-hydroxymarcfortine D;

1-(p-toluenesulfonyl)-14α-hydroxymarcfortine D;

1-acetyl-14α-hydroxymarcfortine D;

1-methyl-14α-hydroxymarcfortine D;

1-benzyl-14α-hydroxymarcfortine D;

1-dimethylcarbamoyl-14α-hydroxymarcfortine D;

1-methoxycarbonyl-14α-hydroxymarcfortine D;

1-acetoxymethyl-14α-hydroxy-14β-methylmarcfortine A;

1-diethoxyphosphoryl-14α-hydroxy-14β-methylmarcfortine A;

1-dimethylsulfamoyl-14α-hydroxy-14β-methylmarcfortine A;

1-cyclopropylcarbonyl-14α-hydroxy-14β-methylmarcfortine A;

2-bicyclo 2.2.1!heptanoyl-14α-hydroxy-14β-methylmarcfortine A;

1-(1-piperidinyl)thiocarbonyl-14α-hydroxy-14β-methylmarcfortine A;

1-succinoyl-14α-hydroxy-14β-methylmarcfortine A;

1-(4-morpholinosulfenyl)-14α-hydroxy-14β-methylmarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-14β-methylmarcfortine A;

24-propoxy-24,25-dihydro-14α-hydroxy-14β-methylmarcfortine A;

1-(p-toluenesulfonyl)-14α-hydroxy-14β-methylmarcfortine A;

1-acetyl-14α-hydroxy-14β-methylmarcfortine A;

1-methyl-14α-hydroxy-14β-methylmarcfortine A;

1-benzyl-14α-hydroxy-14β-methylmarcfortine A;

1-dimethylcarbamoyl-14α-hydroxy-14β-methylmarcfortine A;

1-methoxycarbonyl-14α-hydroxy-14β-methylmarcfortine A;

14α-hydroxy-14β-methylmarcfortine B;

24,25-dihydro-14α-hydroxy-14β-methylmarcfortine B;

24-methoxy-24,25-dihydro-14α-hydroxy-14β-methylmarcfortine B;

1-(p-toluenesulfonyl)-14α-hydroxy-14β-methylmarcfortine B;

1-ethyl-14α-hydroxy-14β-methylmarcfortine B;

1-benzyl-14α-hydroxy-14β-methylmarcfortine B;

18a-ethyl-14α-hydroxy-14β-methylmarcfortine B;

18a-benzyl-14α-hydroxy-14β-methylmarcfortine B;

18a-methoxyethoxymethyl-14α-hydroxy-14β-methylmarcfortine B;

18a-allyl-14α-hydroxy-14β-methylmarcfortine B;

18a-propargyl-14α-hydroxy-14β-methylmarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxy-14β-methylmarcfortine B;

1,18a-bis-ethyl-14α-hydroxy-14β-methylmarcfortine B;

1,18a-bis-benzyl-14α-hydroxy-14β-methylmarcfortine B;

18a-ethyl-24-methoxy-14α-hydroxy-14β-methylmarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxy-14β-methylmarcfortineB;

18a-ethyl-24,25 dihydro-14α-hydroxy-14β-methylmarcfortine B;

24,25-dihydro-14α-hydroxy-14β-methylmarcfortine C;

1-(p-bromobenzene sulfonyl)-14α-hydroxy-14β-methylmarcfortine C;

1-propionyl-14α-hydroxy-14β-methylmarcfortine C;

1-propyl-14α-hydroxy-14β-methylmarcfortine C;

1-benzyl-14α-hydroxy-14β-methylmarcfortine C;

18a-propyl-14α-hydroxy-14β-methylmarcfortine C;

18a-benzyl-14α-hydroxy-14β-methylmarcfortine C;

18a-methoxyethoxymethyl-14α-hydroxy-14β-methylmarcfortine C;

18-allyl-14α-hydroxy-14β-methylmarcfortine C;

18a-propargyl-14α-hydroxy-14β-methylmarcfortine C;

1,18a-bis-propyl-14α-hydroxy-14β-methylmarcfortine C;

1,18a-bis-benzyl-14α-hydroxy-14β-methylmarcfortine C;

14α-hydroxy-14β-methylmarcfortine C;

1-palmitoyl-14α-hydroxy-14β-methylmarcfortine A;

1-(4-morpholinocarbonyl)-14α-hydroxy-14β-methylmarcfortine A;

1-palmitoyl-14α-hydroxy-14β-methylmarcfortine D;

1-(4-morpholinocarbonyl)-14α-hydroxy-14β-methylmarcfortine D;

14α-hydroxy-14β-methylmarcfortine D;

1-acetoxymethyl-14α-hydroxy-14β-methylmarcfortine D;

1-diethoxyphosphoryl-14α-hydroxy-14β-methylmarcfortine D;

1-dimethylsulfamoyl-14α-hydroxy-14β-methylmarcfortine D;

1-cyclopropylcarbonyl-14α-hydroxy-14β-methylmarcfortine D;

2-bicyclo 2.2.1!heptanoyl-14α-hydroxy-14β-methylmarcfortine D;

1-(1-piperidinyl)thiocarbonyl-14α-hydroxy-14β-methylmarcfortine D;

1-succinoyl-14α-hydroxy-14β-methylmarcfortine D;

1-(4-morpholinosulfenyl)-14α-hydroxy-14β-methylmarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-14β-methylmarcfortine D;

24-propoxy-24,25-dihydro-14α-hydroxy-14β-methylmarcfortine D;

1-(p-toluenesulfonyl)-14α-hydroxy-14β-methylmarcfortine D;

1-acetyl-14α-hydroxy-14β-methylmarcfortine D;

1-methyl-14α-hydroxy-14β-methylmarcfortine D;

1-benzyl-14α-hydroxy-14β-methylmarcfortine D;

1-dimethylcarbamoyl-14α-hydroxy-14β-ethylmarcfortine D;

1-methoxycarbonyl-14α-hydroxy-14β-ethylmarcfortine D;

1-acetoxymethyl-14α-hydroxy-14β-ethylmarcfortine A;

1-diethoxyphosphoryl-14α-hydroxy-14β-ethylmarcfortine A;

1-dimethylsulfamoyl-14α-hydroxy-14β-ethylmarcfortine A;

1-cyclopropylcarbonyl-14α-hydroxy-14β-ethylmarcfortine A;

2-bicyclo 2.2.1!heptanoyl-14α-hydroxy-14β-ethylmarcfortine A;

1-(1-piperidinyl)thiocarbonyl-14α-hydroxy-14β-ethylmarcfortine A;

1-succinoyl-14α-hydroxy-14β-ethylmarcfortine A;

1-(4-morpholinosulfenyl)-14α-hydroxy-14β-ethylmarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-14β-ethylmarcfortine A;

24-propoxy-24,25-dihydro-14α-hydroxy-14β-ethylmarcfortine A;

1-(p-toluenesulfonyl)-14α-hydroxy-14β-ethylmarcfortine A;

1-acetyl-14α-hydroxy-14β-ethylmarcfortine A;

1-methyl-14α-hydroxy-14β-ethylmarcfortine A;

1-benzyl-14α-hydroxy-14β-ethylmarcfortine A;

1-dimethylcarbamoyl-14α-hydroxy-14β-ethylmarcfortine A;

1-methoxycarbonyl-14α-hydroxy-14β-ethylmarcfortine A;

14α-hydroxy-14β-ethylmarcfortine B;

24,25-dihydro-14α-hydroxy-14β-ethylmarcfortine B;

24-methoxy-24,25-dihydro-14α-hydroxy-14β-ethylmarcfortine B;

1-(p-toluenesulfonyl)-14α-hydroxy-14β-ethylmarcfortine B;

1-ethyl-14α-hydroxy-14β-ethylmarcfortine B;

1-benzyl-14α-hydroxy-14β-ethylmarcfortine B;

18a-ethyl-14α-hydroxy-14β-ethylmarcfortine B;

18a-benzyl-14α-hydroxy-14β-ethylmarcfortine B;

18a-methoxyethoxymethyl-14α-hydroxy-14β-ethylmarcfortine B;

18a-allyl-14α-hydroxy-14β-ethylmarcfortine B;

18a-propargyl-14α-hydroxy-14β-ethylmarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxy-14β-ethylmarcfortine B;

1,18a-bis-ethyl-14α-hydroxy-14β-ethylmarcfortine B;

1,18a-bis-benzyl-14α-hydroxy-14β-ethylmarcfortine B;

18a-ethyl-24-methoxy-14α-hydroxy-14β-ethylmarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxy-14β-ethylmarcfortineB;

18a-ethyl-24,25 dihydro-14α-hydroxy-14β-ethylmarcfortine B;

24,25 dihydro-14α-hydroxy-14β-ethylmarcfortine C;

1-(p-bromobenzene sulfonyl)-14α-hydroxy-14β-ethylmarcfortine C;

1-propionyl-14α-hydroxy-14β-ethylmarcfortine C;

1-propyl-14α-hydroxy-14β-ethylmarcfortine C;

1-benzyl-14α-hydroxy-14β-ethylmarcfortine C;

18a-propyl-14α-hydroxy-14β-ethylmarcfortine C;

18a-benzyl-14α-hydroxy-14β-ethylmarcfortine C;

18a-methoxyethoxymethyl-14α-hydroxy-14β-ethylmarcfortine C;

18-allyl-14α-hydroxy-14β-ethylmarcfortine C;

18a-propargyl-14α-hydroxy-14β-ethylmarcfortine C;

1,18a-bis-propyl-14α-hydroxy-14β-ethylmarcfortine C;

1,18a-bis-benzyl-14α-hydroxy-14β-ethylmarcfortine C;

14α-hydroxy-14β-ethylmarcfortine C;

1-palmitoyl-14α-hydroxy-14β-ethylmarcfortine A;

1-(4-morpholinocarbonyl)-14α-hydroxy-14β-ethylmarcfortine A;

1-palmitoyl-14α-hydroxy-14β-ethylmarcfortine D;

1-(4-morpholinocarbonyl)-14α-hydroxy-14β-ethylmarcfortine D;

14α-hydroxy-14β-ethylmarcfortine D;

1-acetoxymethyl-14α-hydroxy-14β-ethylmarcfortine D;

1-diethoxyphosphoryl-14α-hydroxy-14β-ethylmarcfortine D;

1-dimethylsulfamoyl-14α-hydroxy-14β-ethylmarcfortine D;

1-cyclopropylcarbonyl-14α-hydroxy-14β-ethylmarcfortine D;

2-bicyclo 2.2.1!heptanoyl-14α-hydroxy-14β-ethylmarcfortine D;

1-(1-piperidinyl)thiocarbonyl-14α-hydroxy-14β-ethylmarcfortine D;

1-succinoyl-14α-hydroxy-14β-ethylmarcfortine D;

1-(4-morpholinosulfenyl)-14α-hydroxy-14β-ethylmarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-14β-ethylmarcfortine D;

24-propoxy-24,25-dihydro-14α-hydroxy-14β-ethylmarcfortine D;

1-(p-toluenesulfonyl)-14α-hydroxy-14β-ethylmarcfortine D;

1-acetyl-14α-hydroxy-14β-ethylmarcfortine D;

1-methyl-14α-hydroxy-14β-ethylmarcfortine D;

1-benzyl-14α-hydroxy-14β-ethylmarcfortine D;

1-dimethylcarbamoyl-14α-hydroxy-14β-ethylmarcfortine D;

1-methoxycarbonyl-14α-hydroxy-14β-ethylmarcfortine D;

1-acetoxymethyl-14β-methylmarcfortine A;

1-diethoxyphosphoryl-14β-methylmarcfortine A;

1-dimethylsulfamoyl-14β-methylmarcfortine A;

1-cyclopropylcarbonyl-14β-methylmarcfortine A;

2-bicyclo 2.2.1!heptanoyl-14β-methylmarcfortine A;

1-(1-piperidinyl)thiocarbonyl -14β-methylmarcfortine A;

1-succinoyl-14β-methylmarcfortine A;

1-(4-morpholinosulfenyl)-14β-methylmarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-14β-methylmarcfortine A;

24-propoxy-24,25-dihydro-14β-methylmarcfortine A;

1-(p-toluenesulfonyl)-14β-methylmarcfortine A;

1-acetyl-14β-methylmarcfortine A;

1-methyl-14β-methylmarcfortine A;

1-benzyl-14β-methylmarcfortine A;

1-dimethylcarbamoyl-14β-methylmarcfortine A;

1-methoxycarbonyl-14β-methylmarcfortine A;

14β-methylmarcfortine B;

24,25-dihydro-14β-methylmarcfortine B;

24-methoxy-24,25-dihydro-14β-methylmarcfortine B;

1-(p-toluenesulfonyl)-14β-methylmarcfortine B;

1-ethyl-14β-methylmarcfortine B;

1-benzyl-14β-methylmarcfortine B;

18a-ethyl-14β-methylmarcfortine B;

18a-benzyl-14β-methylmarcfortine B;

18a-methoxyethoxymethyl-14β-methylmarcfortine B;

18a-allyl-14β-methylmarcfortine B;

18a-propargyl-14β-methylmarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-14β-methylmarcfortine B;

1,18a-bis-ethyl-14β-methylmarcfortine B;

1,18a-bis-benzyl-14β-methylmarcfortine B;

18a-ethyl-24-methoxy-14β-methylmarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14β-methylmarcfortine B;

18a-ethyl-24,25 dihydro-14β-methylmarcfortine B;

24,25 dihydro-14β-methylmarcfortine C;

1-(p-bromobenzene sulfonyl)-14β-methylmarcfortine C;

1-propionyl-14β-methylmarcfortine C;

1-propyl-14β-methylmarcfortine C;

1-benzyl-14β-methylmarcfortine C;

18a-propyl-14β-methylmarcfortine C;

18a-benzyl-14β-methylmarcfortine C;

18a-methoxyethoxymethyl-14β-methylmarcfortine C;

18-allyl-14β-methylmarcfortine C;

18a-propargyl-14β-methylmarcfortine C;

1,18a-bis-propyl-14β-methylmarcfortine C;

1,18a-bis-benzyl-14β-methylmarcfortine C;

14β-methylmarcfortine C;

1-palmitoyl-14β-methylmarcfortine A;

1-(4-morpholinocarbonyl)-14β-methylmarcfortine A;

1-palmitoyl-14β-methylmarcfortine D;

1-(4-morpholinocarbonyl)-14β-methylmarcfortine D;

14β-methylmarcfortine D;

1-acetoxymethyl-14β-methylmarcfortine D;

1-diethoxyphosphoryl-14β-methylmarcfortine D;

1-dimethylsulfamoyl-14β-methylmarcfortine D;

1-cyclopropylcarbonyl-14β-methylmarcfortine D;

2-bicyclo 2.2.1!heptanoyl-14β-methylmarcfortine D;

1-(1-piperidinyl)thiocarbonyl-14β-methylmarcfortine D;

1-succinoyl-14β-methylmarcfortine D;

1-(4-morpholinosulfenyl)-14β-methylmarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-14β-methylmarcfortine D;

24-propoxy-24,25-dihydro-14β-methylmarcfortine D;

1-(p-toluenesulfonyl-14β-methylmarcfortine D;

1-acetyl-14β-methylmarcfortine D;

1-methyl-14β-methylmarcfortine D;

1-benzyl-14β-methylmarcfortine D;

1-dimethylcarbamoyl-14β-methylmarcfortine D;

1-methoxycarbonyl-14β-methylmarcfortine D;

1-acetoxymethyl-14β-ethylmarcfortine A;

1-diethoxyphosphoryl-14β-ethylmarcfortine A;

1-dimethylsulfamoyl-14β-ethylmarcfortine A;

1-cyclopropylcarbonyl-14β-ethylmarcfortine A;

2-bicyclo 2.2.1!heptanoyl-14β-ethylmarcfortine A;

1-(1-piperidinyl)thiocarbonyl -14β-ethylmarcfortine A;

1-succinoyl-14β-ethylmarcfortine A;

1-(4-morpholinosulfenyl)-14β-ethylmarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-14β-ethylmarcfortine A;

24-propoxy-24,25-dihydro-14β-ethylmarcfortine A;

1-(p-toluenesulfonyl)-14β-ethylmarcfortine A;

1-acetyl-14β-ethylmarcfortine A;

1-methyl-14β-ethylmarcfortine A;

1-benzyl-14β-ethylmarcfortine A;

1-dimethylcarbamoyl-14β-ethylmarcfortine A;

1-methoxycarbonyl-14β-ethylmarcfortine A;

14β-ethylmarcfortine B;

24,25-dihydro-14β-ethylmarcfortine B;

24-methoxy-24,25-dihydro-14β-ethylmarcfortine B;

1-(p-toluenesulfonyl)-14β-ethylmarcfortine B;

1-ethyl-14β-ethylmarcfortine B;

1-benzyl-14β-ethylmarcfortine B;

18a-ethyl-14β-ethylmarcfortine B;

18a-benzyl-14β-ethylmarcfortine B;

18a-methoxyethoxymethyl-14β-ethylmarcfortine B;

18a-ally-14β-ethylmarcfortine B;

18a-propargyl-14β-ethylmarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-14β-ethylmarcfortine B;

1,18a-bis-ethyl-14β-ethylmarcfortine B;

1,18a-bis-benzyl-14β-ethylmarcfortine B;

18a-ethyl-24-methoxy-14β-ethylmarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14β-ethylmarcfortine B;

18a-ethyl-24,25 dihydro-14β-ethylmarcfortine B;

24,25 dihydro-14β-ethylmarcfortine C;

1-(p-bromobenzene sulfonyl)-14β-ethylmarcfortine C;

1-propionyl-14β-ethylmarcfortine C;

1-propyl-14β-ethylmarcfortine C;

1-benzyl-14β-ethylmarcfortine C;

18a-propyl-14β-ethylmarcfortine C;

18a-benzyl-14β-ethylmarcfortine C;

18a-methoxyethoxymethyl-14β-ethylmarcfortine C;

18-allyl-14β-ethylmarcfortine C;

18a-propargyl-14β-ethylmarcfortine C;

1,18a-bis-propyl-14β-ethylmarcfortine C;

1,18a-bis-benzyl-14β-ethylmarcfortine C;

14β-ethylmarcfortine C;

1-palmitoyl-14β-ethylmarcfortine A;

1-(4-morpholinocarbonyl)-14β-ethylmarcfortine A;

1-palmitoyl-14β-ethylmarcfortine D;

1-(4-morpholinocarbonyl)-14β-ethylmarcfortine D;

14β-ethylmarcfortine D;

1-acetoxymethyl-14β-ethylmarcfortine D;

1-diethoxyphosphoryl-14β-ethylmarcfortine D;

1-dimethylsulfamoyl-14β-ethylmarcfortine D;

1-cyclopropylcarbonyl-14β-ethylmarcfortine D;

2-bicyclo 2.2.1!heptanoyl-14β-ethylmarcfortine D;

1-(1-piperidinyl)thiocarbonyl-14β-ethylmarcfortine D;

1-succinoyl-14β-ethylmarcfortine D;

1-(4-morpholinosulfenyl)-14β-ethylmarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-14β-ethylmarcfortine D;

24-propoxy-24,25-dihydro-14β-ethylmarcfortine D;

1-(p-toluenesulfonyl)-14β-ethylmarcfortine D;

1-acetyl-14β-ethylmarcfortine D;

1-methyl-14β-ethylmarcfortine D;

1-benzyl-14β-ethylmarcfortine D;

1-dimethylcarbamoyl-14β-ethylmarcfortine D;

1-methoxycarbonyl-14β-ethylmarcfortine D;

1-acetoxymethyl-14α-O-methylmarcfortine A;

14α-O-methylmarcfortine A;

14α-O-methyl-14β-methylmarcfortine A;

14α-O-methyl-14β-ethylmarcfortine A;

1-diethoxyphosphoryl-14α-O-methylmarcfortine A;

1-dimethylsulfamoyl-14α-O-methylmarcfortine A;

1-cyclopropylcarbonyl-14α-O-methylmarcfortine A;

2-bicyclo 2.2.1!heptanoyl-14α-O-methylmarcfortine A;

1-(1-piperidinyl)thiocarbonyl-14α-O-methylmarcfortine A;

1-succinoyl-14α-O-methylmarcfortine A;

1-(4-morpholinosulfenyl)-14α-O-methylmarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-14α-O-methylmarcfortine A;

24-propoxy-24,25-dihydro-14α-O-methylmarcfortine A;

1-(p-toluenesulfonyl)-14α-O-methylmarcfortine A;

1-acetyl-14α-O-methylmarcfortine A;

1-methyl-14α-O-methylmarcfortine A;

1-benzyl-14α-O-methylmarcfortine A;

1-dimethylcarbamoyl-14α-O-methylmarcfortine A;

1-methoxycarbonyl-14α-O-methylmarcfortine A;

14α-O-methylmarcfortine B;

24,25-dihydro-14α-O-methylmarcfortine B;

24-methoxy-24,25-dihydro-14α-O-methylmarcfortine B;

1-(p-toluenesulfonyl)-14α-O-methylmarcfortine B;

1-ethyl-14α-O-methylmarcfortine B;

1-benzyl-14α-O-methylmarcfortine B;

18a-ethyl-14α-O-methylmarcfortine B;

18a-benzyl-14α-O-methylmarcfortine B;

18a-methoxyethoxymethyl-14α-O-methylmarcfortine B;

18a-allyl-14α-O-methylmarcfortine B;

18a-propargyl-14α-O-methylmarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-14α-O-methylmarcfortine B;

1,18a-bis-ethyl-14α-O-methylmarcfortine B;

1,18a-bis-benzyl-14α-O-methylmarcfortine B;

18a-ethyl-24-methoxy-14α-O-methylmarcfortine B;

1(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-O-methylmarcfortine B;

18a-ethyl-24,25 dihydro-14α-O-methylmarcfortine B;

24,25 dihydro-14α-O-methylmarcfortine C;

1-(p-bromobenzene sulfonyl)-14α-O-methylmarcfortine C;

1-propionyl-14α-O-methylmarcfortine C;

1-propyl-14α-O-methylmarcfortine C;

1-benzyl-14α-O-methylmarcfortine C;

18a-propyl-14α-O-methylmarcfortine C;

18a-benzyl-14α-O-methylmarcfortine C;

18a-methoxyethoxymethyl-14α-O-methylmarcfortine C;

18-allyl-14α-O-methylmarcfortine C;

18-propargyl-14α-O-methylmarcfortine C;

1,18a-bis-propyl-14α-O-methylmarcfortine C;

1,18a-bis-benzyl-14α-O-methylmarcfortine C;

14α-O-methylmarcfortine C;

1-palmitoyl-14α-O-methylmarcfortine A;

1-(4-morpholinocarbonyl)-14α-O-methylmarcfortine A;

1-palmitoyl-14α-O-methylmarcfortine D;

1-(4-morpholincarbonyl)-14α-O-methylmarcfortine D;

14α-O-methylmarcfortine D;

1-acetoxymethyl-14α-O-methylmarcfortine D;

1-diethoxyphosphoryl-14α-O-methylmarcfortine D;

1-dimethylsulfamoyl-14α-O-methylmarcfortine D;

1-cyclopropylcarbonyl-14α-O-methylmarcfortine D;

2-bicyclo 2.2.1!-heptanoyl-14α-O-methylmarcfortine D;

1-(1-piperidinyl)thiocarbonyl-14α-O-methylmarcfortine D;

1-succinoyl-14α-O-methylmarcfortine D;

1-(4-morpholinosulfenyl)-14α-O-methylmarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-14α-O-methylmarcfortine D;

24-propoxy-24,25-dihydro-14α-O-methylmarcfortine D;

1-(p-toluenesulfonyl)-14α-O-methylmarcfortine D;

1-acetyl-14α-O-methylmarcfortine D;

1-methyl-14α-O-methylmarcfortine D;

1-benzyl-14α-O-methylmarcfortine D;

1-dimethylcarbamoyl-14α-O-methylmarcfortine D;

1-methoxycarbonyl-14α-O-methylmarcfortine D;

1-acetoxymethyl-14α-O-methyl-14β-methylmarcfortine A;

1-diethoxyphosphoryl-14α-O-methyl-14β-methylmarcfortine A;

1-dimethylsulfamoyl-14α-O-methyl-14β-methylmarcfortine A;

1-cyclopropylcarbonyl-14α-O-methyl-14β-methylmarcfortine A;

2-bicyclo 2.2.1!heptanoyl-14α-O-methyl-14β-methylmarcfortine A;

1-(1-piperidinyl)thiocarbonyl-14α-O-methyl-14β-methylmarcfortine A;

1-succinoyl-14α-O-methyl-14β-methylmarcfortine A;

1-(4-morpholinosulfenyl)-14α-O-methyl-14β-methylmarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-14α-O-methyl-14β-methylmarcfortine A;

24-propoxy-24,25-dihydro-14α-O-methyl-14β-methylmarcfortine A;

1-(p-toluenesulfonyl)-14α-O-methyl-14β-methylmarcfortine A;

1-acetyl-14α-O-methyl-14β-methylmarcfortine A;

1-methyl-14α-O-methyl-14β-methylmarcfortine A;

1-benzyl-14α-O-methyl-14β-methylmarcfortine A;

1-dimethylcarbamoyl-14α-O-methyl-14β-methylmarcfortine A;

1-methoxycarbonyl-14α-O-methyl-14β-methylmarcfortine A;

14α-O-methyl-14β-methylmarcfortine B;

24,25-dihydro-14α-O-methyl-14β-methylmarcfortine B;

24-methoxy-24,25-dihydro-14α-O-methyl-14β-methylmarcfortine B;

1-(p-toluenesulfonyl)-14α-O-methyl-14β-methylmarcfortine B;

1-ethyl-14α-O-methyl-14β-methylmarcfortine B;

1-benzyl-14α-O-methyl-14β-methylmarcfortine B;

18a-ethyl-14α-O-methyl-14β-methylmarcfortine B;

18a-benzyl-14α-O-methyl-14β-methylmarcfortine B;

18a-methoxyethoxymethyl-14α-O-methyl-14β-methylmarcfortine B;

18a-allyl-14α-O-methyl-14β-methylmarcfortine B;

18a-propargyl-14α-O-methyl-14β-methylmarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-14α-O-methyl-14β-methylmarcfortine B;

1,18a-bis-ethyl-14α-O-methyl-14β-methylmarcfortine B;

1,18a-bis-benzyl-14α-O-methyl-14β-methylmarcfortine B;

18a-ethyl-24-methoxy-14α-O-methyl-14β-methylmarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-O-methyl-14β-methylmarcfortineB;

18a-ethyl-24,25 dihydro-14α-O-methyl-14β-methylmarcfortine B;

24,25 dihydro-14α-O-methyl-14β-methylmarcfortine C;

1-(p-bromobenzene sulfonyl)-14α-O-methyl-14β-methylmarcfortine C;

1-propionyl-14α-O-methyl-14β-methylmarcfortine C;

1-propyl-14α-O-methyl-14β-methylmarcfortine C;

1-benzyl-14α-O-methyl-14β-methylmarcfortine C;

18a-propyl-14α-O-methyl-14β-methylmarcfortine C;

18a-benzyl-14α-O-methyl-14β-methylmarcfortine C;

18a-methoxyethoxymethyl-14α-O-methyl-14β-methylmarcfortine C;

18-allyl-14α-O-methyl-14β-methylmarcfortine C;

18a-propargyl-14α-O-methyl-14β-methylmarcfortine C;

1,18a-bis-propyl-14α-O-methyl-14β-methylmarcfortine C;

1,18a-bis-benzyl-14α-O-methyl-14β-methylmarcfortine C;

14α-O-methyl-14β-methylmarcfortine C;

1-palmitoyl-14α-O-methyl-14β-methylmarcfortine A;

1-(4-morpholinocarbonyl)-14α-O-methyl-14β-methylmarcfortine A;

1-palmitoyl-14α-O-methyl-14β-methylmarcfortine D;

1-(4-morpholinocarbonyl)-14α-O-methyl-14β-methylmarcfortine D;

14α-O-methyl-14β-methylmarcfortine D;

1-acetoxymethyl-14α-O-methyl-14β-methylmarcfortine D;

1-diethoxyphosphoryl-14α-O-methyl-14β-methylmarcfortine D;

1-dimethylsulfamoyl-14α-O-methyl-14β-methylmarcfortine D;

1-cyclopropylcarbonyl-14α-O-methyl-14β-methylmarcfortine D;

2-bicyclo 2.2.1!heptanoyl-14α-O-methyl-14β-methylmarcfortine D;

1-(1-piperidinyl)thiocarbonyl-14α-O-methyl-14β-methylmarcfortine D;

1-succinoyl-14α-O-methyl-14β-methylmarcfortine D;

1-(4-morpholinosulfenyl)-14α-O-methyl-14β-methylmarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-14α-O-methyl-14β-methylmarcfortine D;

24-propoxy-24,25-dihydro-14α-O-methyl-14β-methylmarcfortine D;

1-(p-toluenesulfonyl)-14α-O-methyl-14β-methylmarcfortine D;

1-acetyl-14α-O-methyl-14β-methylmarcfortine D;

1-methyl-14α-O-methyl-14β-methylmarcfortine D;

1-benzyl-14α-O-methyl-14β-methylmarcfortine D;

1-dimethylcarbamoyl-14α-O-methyl-14β-ethylmarcfortine D;

1-methoxycarbonyl-14α-O-methyl-14β-ethylmarcfortine D;

1-acetoxymethyl-14α-O-methyl-14β-ethylmarcfortine A;

1-diethoxyphosphoryl-14α-O-methyl-14β-ethylmarcfortine A;

1-dimethylsulfamoyl-14α-O-methyl-14β-ethylmarcfortine A;

1-cyclopropylcarbonyl-14α-O-methyl-14β-ethylmarcfortine A;

2-bicyclo 2.2.1!heptanoyl-14α-O-methyl-14β-ethylmarcfortine A;

1-(1-piperidinyl)thiocarbonyl-14α-O-methyl-14β-ethylmarcfortine A;

1-succinoyl-14α-O-methyl-14β-ethylmarcfortine A;

1-(4-morpholinosulfenyl)-14α-O-methyl-14β-ethylmarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-14α-O-methyl-14β-ethylmarcfortine A;

24-propoxy-24,25-dihydro-14α-O-methyl-14β-ethylmarcfortine A;

1-(p-toluenesulfonyl)-14α-O-methyl-14β-ethylmarcfortine A;

1-acetyl-14α-O-methyl-14β-ethylmarcfortine A;

1-methyl-14α-O-methyl-14β-ethylmarcfortine A;

1-benzyl-14α-O-methyl-14β-ethylmarcfortine A;

1-dimethylcarbamoyl-14α-O-methl-14β-ethylmarcfortine A;

1-methoxycarbonyl-14α-O-methyl-14β-ethylmarcfortine A;

14α-O-methyl-14β-ethylmarcfortine B;

24,25-dihydro-14α-O-methyl-14β-ethylmarcfortine B;

24-methoxy-24,25-dihydro-14α-O-methyl-14β-ethylmarcfortine B;

1-(p-toluenesulfonyl)-14α-O-methyl-14β-ethylmarcfortine B;

1-ethyl-14α-O-methyl-14β-ethylmarcfortine B;

1-benzyl-14α-O-methyl-14β-ethylmarcfortine B;

18a-ethyl-14α-O-methyl-14β-ethylmarcfortine B;

18a-benzyl-14α-O-methyl-14β-ethylmarcfortine B;

18a-methoxyethoxymethyl-14α-O-methyl-14β-ethylmarcfortine B;

18a-allyl-14α-O-methyl-14β-ethylmarcfortine B;

18a-propargyl-14α-O-methyl-14β-ethylmarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-14α-O-methyl-14β-ethylmarcfortine B;

1,18a-bis-ethyl-14α-O-methyl-14β-ethylmarcfortine B;

1,18a-bis-benzyl-14α-O-methyl-14β-ethylmarcfortine B;

18a-ethyl-24-methoxy-14α-O-methyl-14β-ethylmarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-O-methyl-14β-ethylmarcfortineB;

18a-ethyl-24,25 dihydro-14α-O-methyl-14β-ethylmarcfortine B;

24,25 dihydro-14α-O-methyl-14β-ethylmarcfortine C;

1-(p-bromobenzene sulfonyl)-14α-O-methyl-14β-ethylmarcfortine C;

1-propionyl-14α-O-methyl-14β-ethylmarcfortine C;

1-propyl-14α-O-methyl-14β-ethylmarcfortine C;

1-benzyl-14α-O-methyl-14β-ethylmarcfortine C;

18a-propyl-14α-O-methyl-14β-ethylmarcfortine C;

18a-benzyl-14α-O-methyl-14β-ethylmarcfortine C;

18a-methoxyethoxymethyl-14α-O-methyl-14β-ethylmarcfortine C;

18-allyl-14α-O-methyl-14β-ethylmarcfortine C;

18a-propargyl-14α-O-methyl-14β-ethylmarcfortine C;

1,18a-bis-propyl-14α-O-methyl-14β-ethylmarcfortine C;

1,18a-bis-benzyl-14α-O-methyl-14β-ethylmarcfortine C;

14α-O-methyl-14β-ethylmarcfortine C;

1-palmitoyl-14α-O-methyl-14β-ethylmarcfortine A;

1-(4-morpholinocarbonyl)-14α-O-methyl-14β-ethylmarcfortine A;

1-palmitoyl-14α-O-methyl-14β-ethylmarcfortine D;

1-(4-morpholinocarbonyl)-14α-O-methyl-14β-ethylmarcfortine D;

14α-O-methyl-14β-ethylmarcfortine D;

1-acetoxymethyl-14α-O-methyl-14β-ethylmarcfortine D;

1-diethoxyphosphoryl-14α-O-methyl-14β-ethylmarcfortine D;

1-dimethylsulfamoyl-14α-O-methyl-14β-ethylmarcfortine D;

1-cyclopropylcarbonyl-14α-O-methyl-14β-ethylmarcfortine D;

2-bicyclo 2.2.1!heptanoyl-14α-O-methyl-14β-ethylmarcfortine D;

1-(1-piperidinyl)thiocarbonyl-14α-O-methyl-14β-ethylmarcfortine D;

1-succinoyl-14α-O-methyl-14β-ethylmarcfortine D;

1-(4-morpholinosulfenyl)-14α-O-methyl-14β-ethylmarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-14α-O-methyl-14β-ethylmarcfortine D;

24-propoxy-24,25-dihydro-14α-O-methyl-14β-ethylmarcfortine D;

1-(p-toluenesulfonyl)-14α-O-methyl-14β-ethylmarcfortine D;

1-acetyl-14α-O-methyl-14β-ethylmarcfortine D;

1-methyl-14α-O-methyl-14β-ethylmarcfortine D;

1-benzyl-14α-O-methyl-14β-ethylmarcfortine D;

1-dimethylcarbamoyl-14α-O-methyl-14β-ethylmarcfortine D;

1-methoxycarbonyl-14α-O-methyl-14β-ethylmarcfortine D;

1-acetoxymethyl-14α-O-allylmarcfortine A;

14α-O-allylmarcfortine A;

14α-O-allyl-14β-methylmarcfortine A;

14α-O-allyl-14β-ethylmarcfortine A;

1-diethoxyphosphoryl-14α-O-allylmarcfortine A;

1-dimethylsulfamoyl-14α-O-allylmarcfortine A;

1-cyclopropylcarbonyl-14α-O-allylmarcfortine A;

2-bicyclo 2.2.1!heptanoyl-14α-O-allylmarcfortine A;

1-(1-piperidinyl)thiocarbonyl-14α-O-allylmarcfortine A;

1-succinoyl-14α-O-allylmarcfortine A;

1-(4-morpholinosulfenyl)-14α-O-allylmarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-14α-O-allylmarcfortine A;

24-propoxy-24,25-dihydro-14α-O-allylmarcfortine A;

1-(p-toluenesulfonyl)-14α-O-allylmarcfortine A;

1-acetyl-14α-O-allylmarcfortine A;

1-methyl-14α-O-allylmarcfortine A;

1-benzyl-14α-O-allylmarcfortine A;

1-dimethylcarbamoyl-14α-O-allylmarcfortine A;

1-methoxycarbonyl-14α-O-allylmarcfortine A;

14α-O-allylmarcfortine B;

24,25-dihydro-14α-O-allylmarcfortine B;

24-methoxy-24,25-dihydro-14α-O-allylmarcfortine B;

1-(p-toluenesulfonyl)-14α-O-allylmarcfortine B;

1-ethyl-14α-O-allylmarcfortine B;

1-benzyl-14α-O-allylmarcfortine B;

18a-ethyl-14α-O-allylmarcfortine B;

18a-benzyl-14α-O-allylmarcfortine B;

18a-methoxyethoxymethyl-14α-O-allylmarcfortine B;

18a-allyl-14α-O-allylmarcfortine B;

18a-propargyl-14α-O-allylmarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-14α-O-allylmarcfortine B;

1,18a-bis-ethyl-14α-O-allylmarcfortine B;

1,18a-bis-benzyl-14α-O-allylmarcfortine B;

18a-ethyl-24-methoxy-14α-O-allylmarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-O-allylmarcfortine B;

18a-ethyl-24,25 dihydro-14α-O-allylmarcfortine B;

24,25 dihydro-14α-O-allylmarcfortine C;

1-(p-bromobenzene sulfonyl)-14α-O-allylmarcfortine C;

1-propionyl-14α-O-allylmarcfortine C;

1-propyl-14α-O-allylmarcfortine C;

1-benzyl-14α-O-allylmarcfortine C;

18a-propyl-14α-O-allylmarcfortine C;

18a-benzyl-14α-O-allylmarcfortine C;

18a-methoxyethoxymethyl-14α-O-allylmarcfortine C;

18-allyl-14α-O-allylmarcfortine C;

18a-propargyl-14α-O-allylmarcfortine C;

1,18a-bis-propyl-14α-O-allylmarcfortine C;

1.18a-bis-benzyl-14α-O-allylmarcfortine C;

14α-O-allylmarcfortine C;

1-palmitoyl-14α-O-allylmarcfortine A;

1-(4-morpholinocarbonyl)-14α-O-allylmarcfortine A;

1-palmitoyl-14α-O-allylmarcfortine D;

1-(4-morpholinocarbonyl)-14α-O-allylmarcfortine D;

14α-O-allylmarcfortine D;

1-acetoxymethyl-14α-O-allylmarcfortine D;

1-diethoxyphosphoryl-14α-O-allylmarcfortine D;

1-dimethylsulfamoyl-14α-O-allylmarcfortine D;

1-cyclopropylcarbonyl-14α-O-allylmarcfortine D;

2-bicyclo 2.2.1!heptanoyl-14α-O-allylmarcfortine D;

1-(1-piperidinyl)thiocarbonyl-14α-O-allylmarcfortine D;

1-succinoyl-14α-O-allylmarcfortine D;

1-(4-morpholinosulfenyl)-14α-O-allylmarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-14α-O-allylmarcfortine D;

24-propoxy-24,25-dihydro-14α-O-allylmarcfortine D;

1-(p-toluenesulfonyl)-14α-O-allylmarcfortine D;

1-acetyl-14α-O-allylmarcfortine D;

1-methyl-14α-O-allylmarcfortine D;

1-benzyl-14α-O-allylmarcfortine D;

1-dimethylcarbamoyl-14α-O-allylmarcfortine D;

1-methoxycarbonyl-14α-O-allylmarcfortine D;

1-acetoxymethyl-14α-O-allyl-14β-methylmarcfortine A;

1-diethoxyphosphoryl-14α-O-allyl-14β-methylmarcfortine A;

1-dimethylsulfamoyl-14α-O-allyl-14β-methylmarcfortine A;

1-cyclopropylcarbonyl-14α-O-allyl-14β-methylmarcfortine A;

2-bicyclo 2.2.1!heptanoyl-14α-O-allyl-14β-methylmarcfortine A;

1-(1-piperidinyl)thiocarbonyl-14α-O-allyl-14β-methylmarcfortine A;

1-succinoyl-14α-O-allyl-14β-methylmarcfortine A;

1-(4-morpholinosulfenyl)-14α-O-allyl-14β-methylmarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-14α-O-allyl-14β-methylmarcfortine A;

24-propoxy-24,25-dihydro-14α-O-allyl-14β-methylmarcfortine A;

1-(p-toluenesulfonyl)-14α-O-allyl-14β-methylmarcfortine A;

1-acetyl-14α-O-allyl-14β-methylmarcfortine A;

1-methyl-14α-O-allyl-14β-methylmarcfortine A;

1-benzyl-14α-O-allyl-14β-methylmarcfortine A;

1-dimethylcarbamoyl-14α-O-allyl-14β-methylmarcfortine A;

1-methoxycarbonyl-14α-O-allyl-14β-methylmarcfortine A;

14α-O-allyl-14β-methylmarcfortine B;

24,25-dihydro-14α-O-allyl-14β-methylmarcfortine B;

24-methoxy-24,25-dihydro-14α-O-allyl-14β-methylmarcfortine B;

1-(p-toluenesulfonyl)-14α-O-allyl-14β-methylmarcfortine B;

1-ethyl-14α-O-allyl-14β-methylmarcfortine B;

1-benzyl-14α-O-allyl-14β-methylmarcfortine B;

18a-ethyl-14α-O-allyl-14β-methylmarcfortine B;

18a-benzyl-14α-O-allyl-14β-methylmarcfortine B;

18a-methoxyethoxymethyl-14α-O-allyl-14β-methylmarcfortine B;

18a-allyl-14α-O-allyl-14β-methylmarcfortine B;

18a-propargyl-14α-O-allyl-14β-methylmarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-14α-O-allyl-14β-methylmarcfortine B;

1,18a-bis-ethyl-14α-O-allyl-14β-methylmarcfortine B;

1,18a-bis-benzyl-14α-O-allyl-14β-methylmarcfortine B;

18a-ethyl-24-methoxy-14α-O-allyl-14β-methylmarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-O-allyl-14β-methylmarcfortineB;

18a-ethyl-24,25 dihydro-14α-O-allyl-14β-methylmarcfortine B;

24,25 dihydro-14α-O-allyl-14β-methylmarcfortine C;

1-(p-bromobenzene sulfonyl)-14α-O-allyl-14β-methylmarcfortine C;

1-propionyl-14α-O-allyl-14β-methylmarcfortine C;

1-propyl-14α-O-allyl-14β-methylmarcfortine C;

1-benzyl-14α-O-allyl-14β-methylmarcfortine C;

18a-propyl-14α-O-allyl-14β-methylmarcfortine C;

18a-benzyl-14α-O-allyl-14β-methylmarcfortine C;

18a-methoxyethoxymethyl-14α-O-allyl-14β-methylmarcfortine C;

18-allyl-14α-O-allyl-14β-methylmarcfortine C;

18a-propargyl-14α-O-allyl-14β-methylmarcfortine C;

1,18a-bis-propyl-14α-O-allyl-14β-methylmarcfortine C;

1,18-a-bis-benzyl-14α-O-allyl-14β-methylmarcfortine C;

14α-O-allyl-14β-methylmarcfortine C;

1-palmitoyl-14α-O-allyl-14β-methylmarcfortine A;

1-(4-morpholinocarbonyl)-14α-O-allyl-14β-methylmarcfortine A;

1-palmitoyl-14α-O-allyl-14β-methylmarcfortine D;

1-(4-morpholinocarbonyl)-14α-O-allyl-14β-methylmarcfortine D;

14α-O-allyl-14β-methylmarcfortine D;

1-acetoxymethyl-14α-O-allyl-14β-methylmarcfortine D;

1-diethoxyphosphoryl-14α-O-allyl-14β-methylmarcfortine D;

1-dimethylsulfamoyl-14α-O-allyl-14β-methylmarcfortine D;

1-cyclopropylcarbonyl-14α-O-allyl-14β-methylmarcfortine D;

2-bicyclo 2.2.1!heptanoyl-14α-O-allyl-14β-methylmarcfortine D;

1-(1-piperidinyl)thiocarbonyl-14α-O-allyl-14β-methylmarcfortine D;

1-succinoyl-14α-O-allyl-14β-methylmarcfortine D;

1(4-morpholinosulfenyl)-14α-O-allyl-14β-methylmarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-14α-O-allyl-14β-methylmarcfortine D;

24-propoxy-24,25-dihydro-14α-O-allyl-14β-methylmarcfortine D;

1-(p-toluenesulfonyl)-14α-O-allyl-14β-methylmarcfortine D;

1-acetyl-14α-O-allyl-14β-methylmarcfortine D;

1-methyl-14α-O-allyl-14β-methylmarcfortine D;

1-benzyl-14α-O-allyl-14β-methylmarcfortine D;

1-dimethylcarbamoyl-14α-O-allyl-14β-ethylmarcfortine D;

1-methoxycarbonyl-14α-O-allyl-14β-ethylmarcfortine D;

1-acetoxymethyl-14α-O-allyl-14β-ethylmarcfortine A;

1-diethoxyphosphoryl-14α-O-allyl-14β-ethylmarcfortine A;

1-dimethylsulfamoyl-14α-O-allyl-14β-ethylmarcfortine A;

1-cyclopropylcarbonyl-14α-O-allyl-14β-ethylmarcfortine A;

2-bicyclo 2.2.1!heptanoyl-14α-O-allyl-14β-ethylmarcfortine A;

1(1-piperidinyl)thiocarbonyl-14α-O-allyl-14β-ethylmarcfortine A;

1-succinoyl-14α-O-allyl-14β-ethylmarcfortine A;

1-(4-morpholinosulfenyl)-14α-O-allyl-14β-ethylmarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-14α-O-allyl-14β-ethylmarcfortine A;

24-propoxy-24,25-dihydro-14α-O-allyl-14β-ethylmarcfortine A;

1-(p-toluenesulfonyl)-14α-O-allyl-14β-ethylmarcfortine A;

1-acetyl-14α-O-allyl-14β-ethylmarcfortine A;

1-methyl-14α-O-allyl-14β-ethylmarcfortine A;

1-benzyl-14α-O-allyl-14β-ethylmarcfortine A;

1-dimethylcarbamoyl-14α-O-allyl-14β-ethylmarcfortine A;

1-methoxycarbonyl-14α-O-allyl-14β-ethylmarcfortine A;

14α-O-allyl-14β-ethylmarcfortine B;

24,25-dihydro-14α-O-allyl-14β-ethylmarcfortine B;

24-methoxy-24,25-dihydro-14α-O-allyl-14β-ethylmarcfortine B;

1-(p-toluenesulfonyl)-14α-O-allyl-14β-ethylmarcfortine B;

1-ethyl-14α-O-allyl-14β-ethylmarcfortine B;

1-benzyl-14α-O-allyl-14β-ethylmarcfortine B;

18a-ethyl-14α-O-allyl-14β-ethylmarcfortine B;

18a-benzyl-14α-O-allyl-14β-ethylmarcfortine B;

18a-methoxyethoxymethyl-14α-O-allyl-14β-ethylmarcfortine B;

18a-allyl-14α-O-allyl-14β-ethylmarcfortine B;

18a-propargyl-14α-O-allyl-14β-ethylmarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-14α-O-allyl-14β-ethylmarcfortine B;

1,18a-bis-ethyl-14α-O-allyl-14β-ethylmarcfortine B;

1,18a-bis-benzyl-14α-O-allyl-14β-ethylmarcfortine B;

18a-ethyl-24-methoxy-14α-O-allyl-14β-ethylmarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-O-allyl-14β-ethylmarcfortineB;

18a-ethyl-24,25 dihydro-14α-O-allyl-14β-ethylmarcfortine B;

24,25 dihydro-14α-O-allyl-14β-ethylmarcfortine C;

1-(p-bromobenzene sulfonyl)-14α-O-allyl-14β-ethylmarcfortine C;

1-propionyl-14α-O-allyl-14β-ethylmarcfortine C;

1-propyl-14α-O-allyl-14β-ethylmarcfortine C;

1-benzyl-14α-O-allyl-14β-ethylmarcfortine C;

18a-propyl-14α-O-allyl-14β-ethylmarcfortine C;

18a-benzyl-14α-O-allyl-14β-ethylmarcfortine C;

18a-methoxyethoxymethyl-14α-O-allyl-14β-ethylmarcfortine C;

18-allyl-14α-O-allyl-14β-ethylmarcfortine C;

18a-propargyl-14α-O-allyl-14β-ethylmarcfortine C;

1,18a-bis-propyl-14α-O-allyl-14β-ethylmarcfortine C;

1,18a-bis-benzyl-14α-O-allyl-14β-ethylmarcfortine C;

14α-O-allyl-14β-ethylmarcfortine C;

1-palmitoyl-14α-O-allyl-14β-ethylmarcfortine A;

1-(4-morpholinocarbonyl)-14α-O-allyl-14β-ethylmarcfortine A;

1-palmitoyl-14α-O-allyl-14β-ethylmarcfortine D;

1-(4-morpholinocarbonyl)-14α-O-allyl-14β-ethylmarcfortine D;

14α-O-allyl-14β-ethylmarcfortine D;

1-acetoxymethyl-14α-O-allyl-14β-ethylmarcfortine D;

1-diethoxyphosphoryl-14α-O-allyl-14β-ethylmarcfortine D;

1-dimethylsulfamoyl-14α-O-allyl-14β-ethylmarcfortine D;

1-cyclopropylcarbonyl-14α-O-allyl-14β-ethylmarcfortine D;

2-bicyclo 2.2.1!heptanoyl-14α-O-allyl-14β-ethylmarcfortine D;

1-(1-piperidinyl)thiocarbonyl-14α-O-allyl-14β-ethylmarcfortine D;

1-succinoyl-14α-O-allyl-14β-ethylmarcfortine D;

1-(4-morpholinosulfenyl)-14α-O-allyl-14β-ethylmarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-14α-O-allyl-14β-ethylmarcfortine D;

24-propoxy-24,25-dihydro-14α-O-allyl-14β-ethylmarcfortine D;

1-(p-toluenesulfonyl)-14α-O-allyl-14β-ethylmarcfortine D;

1-acetyl-14α-O-allyl-14β-ethylmarcfortine D;

1-methyl-14α-O-allyl-14β-ethylmarcfortine D;

1-benzyl-14α-O-allyl-14β-ethylmarcfortine D;

1-dimethylcarbamoyl-14α-O-allyl-14β-ethylmarcfortine D;

1-methoxycarbonyl-14α-O-allyl-14β-ethylmarcfortine D;

14α-hydroxy-14β-methyl-15α-methylmarcfortine A;

1-acetoxymethyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;

1-diethoxyphosphoryl-14α-hydroxy-14β-methyl-15α-methylxymarcfortine A;

1-dimethylsulfamoyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;

1-cyclopropylcarbonyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;

2-bicyclo 2.2.1!heptanoyl-14α-hydroxy-14β-methyl-15α-methylmarcfortineA;

1-(1-piperidinyl)thiocarbonyl-14α-hydroxy-14β-methyl-15α-methylmarcfortineA;

1-succinoyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;

1-(4-morpholinosulfenyl)-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-14β-methyl-15α-methylmarcfortineA;

24-propoxy-24,25-dihydro-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;

1-(p-toluenesulfonyl)-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;

1-acetyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;

1-methyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;

1-benzyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;

1-dimethylcarbamoyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;

1-methoxycarbonyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;

14α-hydroxy-14β-methyl-15α-methylmarcfortine B;

24,25-dihydro-14α-hydroxy-14β-methyl-15α-methylmarcfortine B;

24-methoxy-24,25-dihydro-14α-hydroxy-14β-methyl-15α-methylmarcfortine B;

1-(p-toluenesulfonyl)-14α-hydroxy-14β-methyl-15α-methylmarcfortine B;

1-ethyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine B;

1-benzyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine B;

18a-ethyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine B;

18a-benzyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine B;

18a-methoxyethoxymethyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine B;

18a-allyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine B;

18a-propargyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxy-14β-methyl-15.alpha.-methylmarcfortineB;

1,18a-bis-ethyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine B;

1,18a-bis-benzyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine B;

18a-ethyl-24-methoxy-14α-hydroxy-14β-methyl-15α-methylmarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxymarcfortine B;

18a-ethyl-24,25 dihydro-14α-hydroxy-14β-methyl-15α-methylmarcfortine B;

24,25 dihydro-14α-hydroxy-14β-methyl-15α-methylmarcfortine C;

1-(p-bromobenzene sulfonyl)-14α-hydroxy-14β-methyl-15α-methylmarcfortineC;

1-propionyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine C;

1-propyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine C;

1-benzyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine C;

18a-propyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine C;

18a-benzyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine C;

18a-methoxyethoxymethyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine C;

18-allyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine C;

18a-propargyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine C;

1,18a-bis-propyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine C;

1,18a-bis-benzyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine C;

14α-hydroxy-14β-methyl-15α-methylmarcfortine C;

1-(4-carbethoxy-1,3-thiazolidinin-3-yl)carbonyl-14α-hydroxy-14β-methyl-15α-methylmarcfortineA;

1-palmitoyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;

1-(4-morpholinocarbonyl)-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;

1-palmitoyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine D;

1-(4-morpholinocarbonyl)-14α-hydroxy-14β-methyl-15α-methylmarcfortine D;

14α-hydroxy-14β-methyl-15α-methylmarcfortine D;

1-acetoxymethyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine D;

1-diethoxyphosphoryl-14α-hydroxy-14β-methyl-15α-methylmarcfortine D;

1-dimethylsulfamoyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine D;

1-cyclopropylcarbonyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine D;

2-bicyclo 2.2.1!heptanoyl-14α-hydroxy-14β-methyl-15α-methylmarcfortineD;

1-(1-piperidinyl)thiocarbonyl-14α-hydroxy-14β-methyl-15α-methylmarcfortineD;

1-succinoyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine D;

1-(4-morpholinosulfenyl)-14α-hydroxy-14β-methyl-15α-methylmarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-14β-methyl-15α-methylmarcfortineD;

24-propoxy-24,25-dihydro-14α-hydroxy-14β-methyl-15α-methylmarcfortine D;

1-(p-toluenesulfonyl)-14α-hydroxy-14β-methyl-15α-methylmarcfortine D;

1-acetyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine D;

1-methyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine D;

1-benzyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine D;

1-dimethylcarbamoyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine D;

1-methoxycarbonyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine D;

-14α-hydroxy-15α-methylmarcfortine A;

1-acetoxymethyl-14α-hydroxy-15α-methylmarcfortine A;

1-diethoxyphosphoryl-14α-hydroxy-15α-methylmarcfortine A;

1-dimethylsulfamoyl-14α-hydroxy-15α-methylmarcfortine A;

1-cyclopropylcarbonyl-14α-hydroxy-15α-methylmarcfortine A;

2-bicyclo 2.2.1!heptanoyl-14α-hydroxy-15α-methylmarcfortine A;

1-(1-piperidinyl)thiocarbonyl-14α-hydroxy-15α-methylmarcfortine A;

1-succinoyl-14α-hydroxy-15α-methylmarcfortine A;

1-(4-morpholinosulfenyl)-14α-hydroxy-15α-methylmarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-15α-methylmarcfortine A;

24-propoxy-24,25-dihydro-14α-hydroxy-15α-methylmarcfortine A;

1-(p-toluenesulfonyl)-14α-hydroxy-15α-methylmarcfortine A;

1-acetyl-14α-hydroxy-15α-methylmarcfortine A;

1-methyl-14α-hydroxy-15α-methylmarcfortine A;

1-benzyl-14α-hydroxy-15α-methylmarcfortine A;

1-dimethylcarbamoyl-14α-hydroxy-15α-methylmarcfortine A;

1-methoxycarbonyl-14α-hydroxy-15α-methylmarcfortine A;

14α-hydroxy-15α-methylmarcfortine B;

24,25-dihydro-14α-hydroxy-15α-methylmarcfortine B;

24-methoxy-24,25-dihydro-14α-hydroxy-15α-methylmarcfortine B;

1-(p-toluenesulfonyl)-14α-hydroxy-15α-methylmarcfortine B;

1-ethyl-14α-hydroxy-15α-methylmarcfortine B;

1-benzyl-14α-hydroxy-15α-methylmarcfortine B;

18a-ethyl-14α-hydroxy-15α-methylmarcfortine B;

18a-benzyl-14α-hydroxy-15α-methylmarcfortine B;

18a-methoxyethoxymethyl-14α-hydroxy-15α-methylmarcfortine B;

18a-allyl-14α-hydroxy-15α-methylmarcfortine B;

18a-propargyl-14α-hydroxy-15α-methylmarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxy-15α-methylmarcfortine B;

1,18a-bis-ethyl-14α-hydroxy-15α-methylmarcfortine B;

1,18a-bis-benzyl-14α-hydroxy-15α-methylmarcfortine B;

18a-ethyl-24-methoxy-14α-hydroxy-15α-methylmarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxymarcfortine B;

18a-ethyl-24,25 dihydro-14α-hydroxy-15α-methylmarcfortine B;

24,25 dihydro-14α-hydroxy-15α-methylmarcfortine C;

1-(p-bromobenzene sulfonyl)-14α-hydroxy-15α-methylmarcfortine C;

1-propionyl-14α-hydroxy-15α-methylmarcfortine C;

1-propyl-14α-hydroxy-15α-methylmarcfortine C;

1-benzyl-14α-hydroxy-15α-methylmarcfortine C;

18a-propyl-14α-hydroxy-15α-methylmarcfortine C;

18a-benzyl-14α-hydroxy-15α-methylmarcfortine C;

18a-methoxyethoxymethyl-14α-hydroxy-15α-methylmarcfortine C;

18-allyl-14α-hydroxy-15α-methylmarcfortine C;

18a-propargyl-14α-hydroxy-15α-methylmarcfortine C;

1,18a-bis-propyl-14α-hydroxy-15α-methylmarcfortine C;

1,18a-bis-benzyl-14α-hydroxy-15α-methylmarcfortine C;

14α-hydroxy-15α-methylmarcfortine C;

1(4-carbethoxy-1,3-thiazolidinin-3-yl)carbonyl-14α-hydroxy-15α-methylmarcfortineA;

1-palmitoyl-14α-hydroxy-15α-methylmarcfortine A;

1-(4-morpholinocarbonyl)-14α-hydroxy-15α-methylmarcfortine A;

1-palmitoyl-14α-hydroxy-15α-methylmarcfortine D;

1-(4-morpholinocarbonyl)-14α-hydroxy-15α-methylmarcfortine D;

14α-hydroxy-15α-methylmarcfortine D;

1-acetoxymethyl-14α-hydroxy-15α-methylmarcfortine D;

1-diethoxyphosphoryl-14α-hydroxy-15α-methylmarcfortine D;

1-dimethylsulfamoyl-14α-hydroxy-15α-methylmarcfortine D;

1-cyclopropylcarbonyl-14α-hydroxy-15α-methylmarcfortine D;

2-bicyclo 2.2.1!heptanoyl-14α-hydroxy-15α-methylmarcfortine D;

1-(1-piperidinyl)thiocarbonyl-14α-hydroxy-15α-methylmarcfortine D;

1-succinoyl-14α-hydroxy-15α-methylmarcfortine D;

1-(4-morpholinosulfenyl)-14α-hydroxy-15α-methylmarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-15α-methylmarcfortine D;

24-propoxy-24,25-dihydro-14α-hydroxy-15α-methylmarcfortine D;

1-(p-toluenesulfonyl)-14α-hydroxy-15α-methylmarcfortine D;

1-acetyl-14α-hydroxy-15α-methylmarcfortine D;

1-methyl-14α-hydroxy-15α-methylmarcfortine D;

1-benzyl-14α-hydroxy-15α-methylmarcfortine D;

1-dimethylcarbamoyl-14α-hydroxy-15α-methylmarcfortine D; and

1-methoxycarbonyl-14α-hydroxy-15α-methylmarcfortine D.

The novel compounds of this invention are prepared by the followingchemical reactions which, as examples, are applied to the preparation of14α-hydroxymarcfortine A (Formula 10, Chart A),14α-hydroxy-14β-methylmarcfortine A (Formula 15, Chart C),14β-hydroxymarcfortine A (Formula 17, Chart D), 14α-hydroxymarcfortine AN-oxide (Formula 18, Chart D), 14α-hydroxy-14β-ethylmarcfortine A(Formula 19, Chart D), 14β-methylmarcfortine A14α-hydroxy-14β-methyl-14α-methylmarcfortine A,14α-hydroxy-15α-methylmarcfortine A, and their precursors (Chart Athrough G).

The novel compounds of this invention are prepared by the followingprocedures: It has been found, unexpectedly, that treatment of theMarcfortines A, B, C and D, or suitably substituted C-24, C-25, N-1 andN-18a derivatives thereof, with cyanogen iodide provides a means ofproducing the compounds of the present invention as illustrated byCharts A.

Another aspect of the present invention are the novel intermediatesprepared in accordance with Chart A through G, including:

16-iodo-17-cyanomarcfortine A;

1-acetoxymethyl-16-iodo-17-cyanomarcfortine A;

1-diethoxyphosphoryl-16-iodo-17-cyanomarcfortine A;

1-dimethylsulfamoyl-16-iodo-17-cyanomarcfortine A;

1-cyclopropylcarbonyl-16-iodo-17-cyanomarcfortine A;

2-bicyclo 2.2.1!heptanoyl-16-iodo-17-cyanomarcfortine A;

1-(1-piperidinyl)thiocarbonyl-16-iodo-17-cyanomarcfortine A;

1-succinoyl-16-iodo-17-cyanomarcfortine A;

1-(4-morpholinosulfenyl)-16-iodo-17-cyanomarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-16-iodo-17-cyanomarcfortine A;

24-propoxy-24,25-dihydro-16-iodo-17-cyanomarcfortine A;

1-(p-toluenesulfonyl)-16-iodo-17-cyanomarcfortine A;

1-acetyl-16-iodo-17-cyanomarcfortine A;

1-methyl-16-iodo-17-cyanomarcfortine A;

1-benzyl-16-iodo-17-cyanomarcfortine A;

1-dimethylcarbamoyl-16-iodo-17-cyanomarcfortine A;

1-methoxycarbonyl-16-iodo-17-cyanomarcfortine A;

16-iodo-17-cyanomarcfortine B;

24,25-dihydro-16-iodo-17-cyanomarcfortine B;

24-methoxy-24,25-dihydro-16-iodo-17-cyanomarcfortine B;

1-(p-toluenesulfonyl)-16-iodo-17-cyanomarcfortine B;

1-ethyl-16-iodo-17-cyanomarcfortine B;

1-benzyl-16-iodo-17-cyanomarcfortine B;

18a-ethyl-16-iodo-17-cyanomarcfortine B;

18a-benzyl-16-iodo-17-cyanomarcfortine B;

18a-methoxyethoxymethyl-16-iodo-17-cyanomarcfortine B;

18a-allyl-16-iodo-17-cyanomarcfortine B;

18a-propargyl-16-iodo-17-cyanomarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-16-iodo-17-cyanomarcfortine B;

1,18a-bis-ethyl-16-iodo-17-cyanomarcfortine B;

1,18a-bis-benzyl-16-iodo-17-cyanomarcfortine B;

18a-ethyl-24-methoxy-16-iodo-17-cyanomarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-16-iodo-17-cyanomarcfortineB;

18a-ethyl-24,25 dihydro-16-iodo-17-cyanomarcfortine B;

24,25 dihydro-16-iodo-17-cyanomarcfortine C;

1-(p-bromobenzene sulfonyl)-16-iodo-17-cyanomarcfortine C;

1-propionyl-16-iodo-17-cyanomarcfortine C;

1-propyl-16-iodo-17-cyanomarcfortine C;

1-benzyl-16-iodo-17-cyanomarcfortine C;

18a-propyl-16-iodo-17-cyanomarcfortine C;

18a-benzyl-16-iodo-17-cyanomarcfortine C;

18a-methoxyethoxymethyl-16-iodo-17-cyanomarcfortine C;

18-allyl-16-iodo-17-cyanomarcfortine C;

18a-propargyl-16-iodo-17-cyanomarcfortine C;

1,18a-bis-propyl-16-iodo-17-cyanomarcfortine C;

1,18a-bis-benzyl-16-iodo-17-cyanomarcfortine C;

16-iodo-17-cyanomarcfortine C;

1-(4-carbethoxy-1,3-thiazolidinin-3-yl)carbonyl-16-iodo-17-cyanomarcfortineA;

1-palmitoyl-16-iodo-17-cyanomarcfortine A;

1-(4-morpholinocarbonyl)-16-iodo-17-cyanomarcfortine A;

1-palmitoyl-16-iodo-17-cyanomarcfortine D;

1-(4-morpholinocarbonyl)-16-iodo-17-cyanomarcfortine D;

16-iodo-17-cyanomarcfortine D;

1-acetoxymethyl-16-iodo-17-cyanomarcfortine D;

1-diethoxyphosphoryl-16-iodo-17-cyanomarcfortine D;

1-dimethylsulfamoyl-16-iodo-17-cyanomarcfortine D;

1-cyclopropylcarbonyl-16-iodo-17-cyanomarcfortine D;

2-bicyclo 2.2.1!heptanoyl-16-iodo-17-cyanomarcfortine D;

1-(1-piperidinyl)thiocarbonyl-16-iodo-17-cyanomarcfortine D;

1-succinoyl-16-iodo-17-cyanomarcfortine D;

1-(4-morpholinosulfenyl)-16-iodo-17-cyanomarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-16-iodo-17-cyanomarcfortine D;

24-propoxy-24,25-dihydro-16-iodo-17-cyanomarcfortine D;

1-(p-toluenesulfonyl)-16-iodo-17-cyanomarcfortine D;

1-acetyl-16-iodo-17-cyanomarcfortine D;

1-methyl-16-iodo-17-cyanomarcfortine D;

1-benzyl-16-iodo-17-cyanomarcfortine D;

1-dimethylcarbamoyl-16-iodo-17-cyanomarcfortine D;

1-methoxycarbonyl-16-iodo-17-cyanomarcfortine D;

16,17-dehydro-17-cyanomarcfortine A;

1-acetoxymethyl-16,17-dehydro-17-cyanomarcfortine A;

1-diethoxyphosphoryl-16,17-dehydro-17-cyanomarcfortine A;

1-dimethylsulfamoyl-16,17-dehydro-17-cyanomarcfortine A;

1-cyclopropylcarbonyl-16,17-dehydro-17-cyanomarcfortine A;

2-bicyclo 2.2.1!heptanoyl-16,17-dehydro-17-cyanomarcfortine A;

1-(1-piperidinyl)thiocarbonyl-16,17-dehydro-17-cyanomarcfortine A;

1-succinoyl-16,17-dehydro-17-cyanomarcfortine A;

1-(4-morpholinosulfenyl)-16,17-dehydro-17-cyanomarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-16,17-dehydro-17-cyanomarcfortine A;

24-propoxy-24,25-dihydro-16,17-dehydro-17-cyanomarcfortine A;

1-(p-toluenesulfonyl)-16,17-dehydro-17-cyanomarcfortine A;

1-acetyl-16,17-dehydro-17-cyanomarcfortine A;

1-methyl-16,17-dehydro-17-cyanomarcfortine A;

1-benzyl-16,17-dehydro-17-cyanomarcfortine A;

1-dimethylcarbamoyl-16,17-dehydro-17-cyanomarcfortine A;

1-methoxycarbonyl-16,17-dehydro-17-cyanomarcfortine A;

16,17-dehydro-17-cyanomarcfortine B;

24,25-dihydro-16,17-dehydro-17-cyanomarcfortine B;

24-methoxy-24,25-dihydro-16,17-dehydro-17-cyanomarcfortine B;

1-(p-toluenesulfonyl)-16,17-dehydro-17-cyanomarcfortine B;

1-ethyl-16,17-dehydro-17-cyanomarcfortine B;

1-benzyl-16,17-dehydro-17-cyanomarcfortine B;

18a-ethyl-16,17-dehydro-17-cyanomarcfortine B;

18a-benzyl-16,17-dehydro-17-cyanomarcfortine B;

18a-methoxyethoxymethyl-16,17-dehydro-17-cyanomarcfortine B;

18a-allyl-16,17-dehydro-17-cyanomarcfortine B;

18a-propargyl-16,17-dehydro-17-cyanomarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-16,17-dehydro-17-cyanomarcfortine B;

1,18a-bis-ethyl-16,17-dehydro-17-cyanomarcfortine B;

1,18a-bis-benzyl-16,17-dehydro-17-cyanomarcfortine B;

18a-ethyl-24-methoxy-16,17-dehydro-17-cyanomarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-16,17-dehydro-17-cyanomarcfortineB;

18a-ethyl-24,25 dihydro-16,17-dehydro-17-cyanomarcfortine B;

24,25 dihydro-16,17-dehydro-17-cyanomarcfortine C;

1-(p-bromobenzene sulfonyl)-16,17-dehydro-17-cyanomarcfortine C;

1-propionyl-16,17-dehydro-17-cyanomarcfortine C;

1-propyl-16,17-dehydro-17-cyanomarcfortine C;

1-benzyl-16,17-dehydro-17-cyanomarcfortine C;

18a-propyl-16,17-dehydro-17-cyanomarcfortine C;

18a-benzyl-16,17-dehydro-17-cyanomarcfortine C;

18a-methoxyethoxymethyl-16,17-dehydro-17-cyanomarcfortine C;

18-allyl-16,17-dehydro-17-cyanomarcfortine C;

18a-propargyl-16,17-dehydro-17-cyanomarcfortine C;

1,18a-bis-propyl-16,17-dehydro-17-cyanomarcfortine C;

1,18a-bis-benzyl-16,17-dehydro-17-cyanomarcfortine C;

16,17-dehydro-17-cyanomarcfortine C;

1-(4-carbethoxy-1,3-thiazolidinin-3-yl)carbonyl-16,17-dehydro-17-cyanomarcfortineA;

1-paliitoyl-16,17-dehydro-17-cyanomarcfortine A;

1-(4-morpholinocarbonyl)-16,17-dehydro-17-cyanomarcfortine A;

1-palmitoyl-16,17-dehydro-17-cyanomarcfortine D;

1-(4-morpholinocarbonyl)-16,17-dehydro-17-cyanomarcfortine D;

16,17-dehydro-17-cyanomarcfortine D;

1-acetoxymethyl-16,17-dehydro-17-cyanomarcfortine D;

1-diethoxyphosphoryl-16,17-dehydro-17-cyanomarcfortine D;

1-dimethylsulfamoyl-16,17-dehydro-17-cyanomarcfortine D;

1-cyclopropylcarbonyl-16,17-dehydro-17-cyanomarcfortine D;

2-bicyclo 2.2.1!heptanoyl-16,17-dehydro-17-cyanomarcfortine D;

1-(1 -piperidinyl)thiocarbonyl-16,17-dehydro-17-cyanomarcfortine D;

1-succinoyl-16,17-dehydro-17-cyanomarcfortine D;

1-(4-morpholinosulfenyl)-16,17-dehydro-17-cyanomarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-16,17-dehydro-17-cyanomarcfortine D;

24-propoxy-24,25-dihydro-16,17-dehydro-17-cyanomarcfortine D;

1-(p-toluenesulfonyl)-16,17-dehydro-17-cyanomarcfortine D;

1-acetyl-16,17-dehydro-17-cyanomarcfortine D;

1-methyl-16,17-dehydro-17-cyanomarcfortine D;

1-benzyl-16,17-dehydro-17-cyanomarcfortine D;

1-dimethylcarbamoyl-16,17-dehydro-17-cyanomarcfortine D;

1-methoxycarbonyl-16,17-dehydro-17-cyanomarcfortine D;

17-ketomarcfortine A;

1-acetoxymethyl-17-ketomarcfortine A;

1-diethoxyphosphoryl-17-ketoxymarcfortine A;

1-dimethylsulfamoyl-17-ketomarcfortine A;

1-cyclopropylcarbonyl-17-ketomarcfortine A;

2-bicyclo 2.2.1!heptanoyl-17-ketomarcfortine A;

1-(1-piperidinyl)thiocarbonyl-17-ketomarcfortine A;

1-succinoyl-17-ketomarcfortine A;

1-(4-morpholinosulfenyl)-17-ketomarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-17-ketomarcfortine A;

24-propoxy-24,25-dihydro-17-ketomarcfortine A;

1-(p-toluenesulfonyl)-17-ketomarcfortine A;

1-acetyl-17-ketomarcfortine A;

1-methyl-17-ketomarcfortine A;

1-benzyl-17-ketomarcfortine A;

1-dimethylcarbamoyl-17-ketomarcfortine A;

1-methoxycarbonyl-17-ketomarcfortine A;

17-ketomarcfortine B;

24,25-dihydro-17-ketomarcfortine B;

24-methoxy-24,25-dihydro-17-ketomarcfortine B;

1-(p-toluenesulfonyl)-17-ketomarcfortine B;

1-ethyl-17-ketomarcfortine B;

1-benzyl-17-ketomarcfortine B;

18a-ethyl-17-ketomarcfortine B;

18a-benzyl-17-ketomarcfortine B;

18a-methoxyethoxymethyl-17-ketomarcfortine B;

18a-allyl-17-ketomarcfortine B;

18a-propargyl-17-ketomarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-17-ketomarcfortine B;

1,18a-bis-ethyl-17-ketomarcfortine B;

1,18a-bis-benzyl-17-ketomarcfortine B;

18a-ethyl-24-methoxy-17-ketomarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxymarcfortine B;

18a-ethyl-24,25 dihydro-17-ketomarcfortine B;

24,25 dihydro-17-ketomarcfortine C;

1-(p-bromobenzene sulfonyl)-17-ketomarcfortine C;

1-propionyl-17-ketomarcfortine C;

1-propyl-17-ketomarcfortine C;

1-benzyl-17-ketomarcfortine C;

18a-propyl-17-ketomarcfortine C;

18a-benzyl-17-ketomarcfortine C;

18a-methoxyethoxymethyl-17-ketomarcfortine C;

18-allyl-17-ketomarcfortine C;

18a-propargyl-17-ketomarcfortine C;

1,18a-bis-propyl-17-ketomarcfortine C;

1,18a-bis-benzyJ-17-ketomarcfortine C;

17-ketomarcfortine C;

1-(4-carbethoxy-1,3-thiazolidinin-3-yl)carbonyl-17-ketomarcfortine A;

1-palmitoyl-17-ketomarcfortine A;

1-(4-morpholinocarbonyl)-17-ketomarcfortine A;

1-palmitoyl-17-ketomarcfortine D;

1-(4-morpholinocarbonyl)-17-ketomarcfortine D;

17-ketodroxymarcfortine D;

1-acetoxymethyl-17-ketomarcfortine D;

1-diethoxyphosphoryl-17-ketomarcfortine D;

1-dimethylsulfamoyl-17-ketomarcfortine D;

1-cyclopropylcarbonyl-17-ketomarcfortine D;

2-bicyclo 2.2.1!heptanoyl-17-ketomarcfortine D;

1-(1-piperidinyl)thiocarbonyl-17-ketomarcfortine D;

1-succinoyl-17-ketomarcfortine D;

1-(4-morpholinosulfenyl)-17-ketomarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-17-ketomarcfortine D;

24-propoxy-24,25-dihydro-17-ketomarcfortine D;

1-(p-toluenesulfonyl)-17-ketomarcfortine D;

1-acetyl-17-ketomarcfortine D;

1-methyl-17-ketomarcfortine D;

1-benzyl-17-ketomarcfortine D;

1-dimethylcarbamoyl-17-ketomarcfortine D;

1-methoxycarbonyl-17-ketomarcfortine D;

15,16-dehydro-17-ketomarcfortine A;

1-acetoxymethyl-15,16-dehydro-17-ketomarcfortine A;

1-diethoxyphosphoryl-15,16-dehydro-17-ketoxymarcfortine A;

1-dimethylsulfamoyl-15,16-dehydro-17-ketomarcfortine A;

1-cyclopropylcarbonyl-15,16-dehydro-17-ketomarcfortine A;

2-bicyclo 2.2.1!heptanoyl-15,16-dehydro-17-ketomarcfortine A;

1-(1 -piperidinyl)thiocarbonyl-15,16-dehydro-17-ketomarcfortine A;

1-succinoyl-15,16-dehydro-17-ketomarcfortine A;

1-(4-morpholinosulfenyl)-15,16-dehydro-17-ketomarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-15,16-dehydro-17-ketomarcfortine A;

24propoxy-24,25-dihydro-15,16-dehydro-17-ketomarcfortine A;

1-(p-toluenesulfonyl)-15,16-dehydro-17-ketomarcfortine A;

1-acetyl-15,16-dehydro-17-ketomarcfortine A;

1-methyl-15,16-dehydro-17-ketomarcfortine A;

1-benzyl-15,16-dehydro-17-ketomarcfortine A;

1-dimethylcarbamoyl-15,16-dehydro-17-ketomarcfortine A;

1-methoxycarbonyl-15,16-dehydro-17-ketomarcfortine A;

15,16-dehydro-17-ketomarcfortine B;

24,25-dihydro-15,16-dehydro-17-ketomarcfortine B;

24-methoxy-24,25-dihydro-15,16-dehydro-17-ketomarcfortine B;

1-(p-toluenesulfonyl)-15,16-dehydro-17-ketomarcfortine B;

1-ethyl-15,16-dehydro-17-ketomarcfortine B;

1-benzyl-15,16-dehydro-17-ketomarcfortine B;

18a-ethyl-15,16-dehydro-17-ketomarcfortine B;

18a-benzyl-15,16-dehydro-17-ketomarcfortine B;

18a-methoxyethoxymethyl-15,16-dehydro-17-ketomarcfortine B;

18a-allyl-15,16-dehydro-17-ketomarcfortine B;

18a-propargyl-15,16-dehydro-17-ketomarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-15,16-dehydro-17-ketomarcfortine B;

1,18a-bis-ethyl-15,16-dehydro-17-ketomarcfortine B;

1,18a-bis-benzyl-15,16-dehydro-17-ketomarcfortine B;

18a-ethyl-24-methoxy-15,16-dehydro-17-ketomarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxymarcfortine B;

18a-ethyl-24,25 dihydro-15,16-dehydro-17-ketomarcfortine B;

24,25 dihydro-15,16-dehydro-17-ketomarcfortine C;

1-(p-bromobenzene sulfonyl)-15,16-dehydro-17-ketomarcfortine C;

1-propionyl-15,16-dehydro-17-ketomarcfortine C;

1-propyl-15,16-dehydro-17-ketomarcfortine C;

1-benzyl-15,16-dehydro-17-ketomarcfortine C;

18a-propyl-15,16-dehydro-17-ketomarcfortine C;

18a-benzyl-15,16-dehydro-17-ketomarcfortine C;

18a-methoxyethoxymethyl-15,16-dehydro-17-ketomarcfortine C;

18-allyl-15,16-dehydro-17-ketomarcfortine C;

18a-propargyl-15,16-dehydro-17-ketomarcfortine C;

1,18a-bis-propyl-15,16-dehydro-17-ketomarcfortine C;

1,18a-bis-benzyl-15,16-dehydro-17-ketomarcfortine C;

15,16-dehydro-17-ketomarcfortine C;

1-(4carbethoxy-1,3-thiazolidinin-3-yl)carbonyl-15,16-dehydro-17-ketomarcfortineA;

1-palmitoyl-15,16-dehydro-17-ketomarcfortine A;

1-(4-morpholinocarbonyl)-15,16-dehydro-17-ketomarcfortine A;

1-palmitoyl-15,16-dehydro-17-ketomarcfortine D;

1-(4-morpholinocarbonyl)-15,16-dehydro-17-ketomarcfortine D;

15,16-dehydro-17-ketomarcfortine D;

1-acetoxymethyl-15,16-dehydro-17-ketomarcfortine D;

1-diethoxyphosphoryl-15,16-dehydro-17-ketomarcfortine D;

1-dimethylsulfamoyl-15,16-dehydro-17-ketomarcfortine D;

1-cyclopropylcarbonyl-15,16-dehydro-17-ketomarcfortine D;

2-bicyclo 2.2.1!heptanoyl-15,16-dehydro-17-ketomarcfortine D;

1-(1-piperidinyl)thiocarbonyl-15,16-dehydro-17-ketomarcfortine D;

1-succinoyl-15,16-dehydro-17-ketomarcfortine D;

1-(4-morpholinosulfenyl)-15,16-dehydro-17-ketomarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-15,16-dehydro-17-ketomarcfortine D;

24-propoxy-24,25-dihydro-15,16-dehydro-17-ketomarcfortine D;

1-(p-toluenesulfonyl)-15,16-dehydro-17-ketomarcfortine D;

1-acetyl-15,16-dehydro-17-ketomarcfortine D;

1-methyl-15,16-dehydro-17-ketomarcfortine D;

1-benzyl-15,16-dehydro-17-ketomarcfortine D;

1-dimethylcarbamoyl-15,16-dehydro-17-ketomarcfortine D;

1-methoxycarbonyl-15,16-dehydro-17-ketomarcfortine D;

14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;

1-acetoxymethyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;

1-diethoxyphosphoryl-14α-hydroxy-15,16-dehydro-17-ketoxymarcfortine A;

1-dimethylsulfamoyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;

1-cyclopropylcarbonyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;

2-bicyclo 2.2.1!heptanoyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortineA;

1-(1-piperidinyl)thiocarbonyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortineA;

1-succinoyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;

1-(4-morpholinosulfenyl)-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;

24-propoxy-24,25-dihydro-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;

1-(p-toluenesulfonyl)-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;

1-acetyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;

1-methyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;

1-benzyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;

1-dimethylcarbamoyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;

1-methoxycarbonyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;

14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;

24,25-dihydro-14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;

24-methoxy-24,25-dihydro-14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;

1-(p-toluenesulfonyl)-14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;

1-ethyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;

1-benzyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;

18a-ethyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;

18a-benzyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;

18a-methoxyethoxymethyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;

18a-allyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;

18a-propargyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxy-15,16-dehydro-17-ketomarcfortineB;

1,18a-bis-ethyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;

1,18a-bis-benzyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;

18a-ethyl-24-methoxy-14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxymarcfortine B;

18a-ethyl-24,25 dihydro-14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;

24,25 dihydro-14α-hydroxy-15,16-dehydro-17-ketomarcfortine C;

1-(p-bromobenzene sulfonyl)-14α-hydroxy-15,16-dehydro-17-ketomarcfortineC;

1-propionyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine C;

1-propyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine C;

1-benzyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine C;

18a-propyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine C;

18a-benzyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine C;

18a-methoxyethoxymethyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine C;

18-allyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine C;

18a-propargyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine C;

1,18a-bis-propyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine C;

1,18a-bis-benzyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine C;

14α-hydroxy-15,16-dehydro-17-ketomarcfortine C;

1-(4-carbethoxy-1,3-thiazolidinin-3-yl)carbonyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortineA;

1-palmitoyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;

1-(4-morpholinocarbonyl)-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;

1-palmitoyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine D;

1-(4-morpholinocarbonyl)-14α-hydroxy-15,16-dehydro-17-ketomarcfortine D;

14α-hydroxy-15,16-dehydro-17-ketomarcfortine D;

1-acetoxymethyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine D;

1-diethoxyphosphoryl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine D;

1-dimethylsulfamoyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine D;

1-cyclopropylcarbonyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine D;

2-bicyclo 2.2.1!heptanoyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortineD;

1-(1-piperidinyl)thiocarbonyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortineD;

1-succinoyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine D;

1-(4-morpholinosulfenyl)-14α-hydroxy-15,16-dehydro-17-ketomarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-15,16-dehydro-17-ketomarcfortineD;

24-propoxy-24,25-dihydro-14α-hydroxy-15,16-dehydro-17-ketomarcfortine D;

1-(p-toluenesulfonyl)-14α-hydroxy-15,16-dehydro-17-ketomarcfortine D;

1-acetyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine D;

1-methyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine D;

1-benzyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine D;

1-dimethylcarbamoyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine D;

1-methoxycarbonyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine D;

14α-hydroxy-17-ketomarcfortine A;

1-acetoxymethyl-14α-hydroxy-17-ketomarcfortine A;

1-diethoxyphosphoryl-14α-hydroxy-17-ketoxymarcfortine A;

1-dimethylsulfamoyl-14α-hydroxy-17-ketomarcfortine A;

1-cyclopropylcarbonyl-14α-hydroxy-17-ketomarcfortine A;

2-bicyclo 2.2.1!heptanoyl-14α-hydroxy-17-ketomarcfortine A;

1-(1-piperidinyl)thiocarbonyl-14α-hydroxy-17-ketomarcfortine A;

1-succinoyl-14α-hydroxy-17-ketomarcfortine A;

1-(4-morpholinosulfenyl)-14α-hydroxy-17-ketomarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-17-ketomarcfortine A;

24-propoxy-24,25-dihydro-14α-hydroxy-17-ketomarcfortine A;

1-(p-toluenesulfonyl)-14-α-hydroxy-17-ketomarcfortine A;

1-acetyl-14α-hydroxy-17-ketomarcfortine A;

1-methyl-14α-hydroxy-17-ketomarcfortine A;

1-benzyl-14α-hydroxy-17-ketomarcfortine A;

1-dimethylcarbamoyl-14α-hydroxy-17-ketomarcfortine A;

1-methoxycarbonyl-14α-hydroxy-17-ketomarcfortine A;

14α-hydroxy-17-ketomarcfortine B;

24,25-dihydro-14α-hydroxy-17-ketomarcfortine B;

24-methoxy-24,25-dihydro-14α-hydroxy-17-ketomarcfortine B;

1-(p-toluenesulfonyl)-14α-hydroxy-17-ketomarcfortine B;

1-ethyl-14α-hydroxy-17-ketomarcfortine B;

1-benzyl-14α-hydroxy-17-ketomarcfortine B;

18a-ethyl-14α-hydroxy-17-ketomarcfortine B;

18a-benzyl-14α-hydroxy-17-ketomarcfortine B;

18a-methoxyethoxymethyl-14α-hydroxy-17-ketomarcfortine B;

18a-allyl-14α-hydroxy-17-ketomarcfortine B;

18a-propargyl-14α-hydroxy-17-ketomarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxy-17-ketomarcfortine B;

1,18a-bis-ethyl-14α-hydroxy-17-ketomarcfortine B;

1,18a-bis-benzyl-14α-hydroxy-17-ketomarcfortine B;

18a-ethyl-24-methoxy-14α-hydroxy-17-ketomarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxymarcfortine B;

18a-ethyl-24,25 dihydro-14α-hydroxy-17-ketomarcfortine B;

24,25 dihydro-14α-hydroxy-17-ketomarcfortine C;

1-(p-bromobenzene sulfonyl)-14α-hydroxy-17-ketomarcfortine C;

1-propionyl-14α-hydroxy-17-ketomarcfortine C;

1-propyl-14α-hydroxy-17-ketomarcfortine C;

1-benzyl-14α-hydroxy-17-ketomarcfortine C;

18a-propyl-14α-hydroxy-17-ketomarcfortine C;

18a-benzyl-14α-hydroxy-17-ketomarcfortine C;

18a-methoxyethoxymethyl-14α-hydroxy-17-ketomarcfortine C;

18-allyl-14α-hydroxy-17-ketomarcfortine C;

18a-propargyl-14α-hydroxy-17-ketomarcfortine C;

1,18a-bis-propyl-14α-hydroxy-17-ketomarcfortine C;

1,18a-bis-benzyl-14α-hydroxy-17-ketomarcfortine C;

14α-hydroxy-17-ketomarcfortine C;

1-(4-carbethoxy-1,3-thiazolidinin-3-yl)carbonyl-14α-hydroxy-17-ketomarcfortineA;

1-palmitoyl-14α-hydroxy-17-ketomarcfortine A;

1-(4-morpholinocarbonyl)-14α-hydroxy-17-ketomarcfortine A;

1-palmitoyl-14α-hydroxy-17-ketomarcfortine D;

1-(4-morpholinocarbonyl)-14α-hydroxy-17-ketomarcfortine D;

14α-hydroxy-17-ketomarcfortine D;

1-acetoxymethyl-14α-hydroxy-17-ketomarcfortine D;

1-diethoxyphosphoryl-14α-hydroxy-17-ketomarcfortine D;

1-dimethylsulfamoyl-14α-hydroxy-17-ketomarcfortine D;

1-cyclopropylcarbonyl-14α-hydroxy-17-ketomarcfortine D;

2-bicyclo 2.2.1!heptanoyl-14α-hydroxy-17-ketomarcfortine D;

1-(1-piperidinyl)thiocarbonyl-14α-hydroxy-17-ketomarcfortine D;

1-succinoyl-14α-hydroxy-17-ketomarcfortine D;

1-(4-morpholinosulfenyl)-14α-hydroxy-17-ketomarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-17-ketomarcfortine D;

24-propoxy-24,25-dihydro-14α-hydroxy-17-ketomarcfortine D;

1-(p-toluenesulfonyl)-14α-hydroxy-17-ketomarcfortine D;

1-acetyl-14α-hydroxy-17-ketomarcfortine D;

1-methyl-14α-hydroxy-17-ketomarcfortine D;

1-benzyl-14α-hydroxy-17-ketomarcfortine D;

1-dimethylcarbamoyl-14α-hydroxy-17-ketomarcfortine D;

1-methoxycarbonyl-14α-hydroxy-17-ketomarcfortine D;

14,17-diketomarcfortine A;

1-acetoxymethyl-14,17-diketomarcfortine A;

1-diethoxyphosphoryl-14,17-diketoxymarcfortine A;

1-dimethylsulfamoyl-14,17-diketomarcfortine A;

1-cyclopropylcarbonyl-14,17-diketomarcfortine A;

2-bicyclo 2.2.1!heptanoyl-14,17-diketomarcfortine A;

1-(1 -piperidinyl)thiocarbonyl-14,17-diketomarcfortine A;

1-succinoyl-14,17-diketomarcfortine A;

1-(4-morpholinosulfenyl)-14,17-diketomarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-14,17-diketomarcfortine A;

24-propoxy-24,25-dihydro-14,17-diketomarcfortine A;

1-(p-toluenesulfonyl)-14,17-diketomarcfortine A;

1-acetyl-14,17-diketomarcfortine A;

1-methyl-14,17-diketomarcfortine A;

1-benzyl-14,17-diketomarcfortine A;

1-dimethylcarbamoyl-14,17-diketomarcfortine A;

1-methoxycarbonyl-14,17-diketomarcfortine A;

14,17-diketomarcfortine B;

24,25-dihydro-14,17-diketomarcfortine B;

24-methoxy-24,25-dihydro-14,17-diketomarcfortine B;

1-(p-toluenesulfonyl)-14,17-diketomarcfortine B;

1-ethyl-14,17-diketomarcfortine B;

1-benzyl-14,17-diketomarcfortine B;

18a-ethyl-14,17-diketomarcfortine B;

18a-benzyl-14,17-diketomarcfortine B;

18a-methoxyethoxymethyl-14,17-diketomarcfortine B;

18a-allyl-14,17-diketomarcfortine B;

18a-propargyl-14,17-diketomarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-14,17-diketomarcfortine B;

1,18a-bis-ethyl-14,17-diketomarcfortine B;

1,18a-bis-benzyl-14,17-diketomarcfortine B;

18a-ethyl-24-methoxy-14,17-diketomarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxymarcfortine B;

18a-ethyl-24,25 dihydro-14,17-diketomarcfortine B;

24,25 dihydro-14,17-diketomarcfortine C;

1-(p-bromobenzene sulfonyl)-14,17-diketomarcfortine C;

1-propionyl-14,17-diketomarcfortine C;

1-propyl-14,17-diketomarcfortine C;

1-benzyl-14,17-diketomarcfortine C;

18a-propyl-14,17-diketomarcfortine C;

18a-benzyl-14,17-diketomarcfortine C;

18a-methoxyethoxymethyl-14,17-diketomarcfortine C;

18-allyl-14,17-diketomarcfortine C;

18a-propargyl-14,17-diketomarcfortine C;

1,18a-bis-propyl-14,17-diketomarcfortine C;

1,18a-bis-benzyl-14,17-diketomarcfortine C;

14,17-diketomarcfortine C;

1-(4-carbethoxy-1,3-thiazolidinin-3-yl)carbonyl-14,17-diketomarcfortineA;

1-palmitoyl-14,17-diketomarcfortine A;

1-(4-morpholinocarbonyl)-14,17-diketomarcfortine A;

1-palmitoyl-14,17-diketomarcfortine D;

1-(4-morpholinocarbonyl)-14,17-diketomarcfortine D;

14,17-diketomarcfortine D;

1-acetoxymethyl-14,17-diketomarcfortine D;

1-diethoxyphosphoryl-14,17-diketomarcfortine D;

1-dimethylsulfamoyl-14,17-diketomarcfortine D;

1-cyclopropylcarbonyl-14,17-diketomarcfortine D;

2-bicyclo 2.2.1!heptanoyl-14,17-diketomarcfortine D;

1-(1-piperidinyl)thiocarbonyl-14,17-diketomarcfortine D;

1-succinoyl-14,17-diketomarcfortine D;

1-(4-morpholinosulfenyl)-14,17-diketomarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-14,17-diketomarcfortine D;

24-propoxy-24,25-dihydro-14,17-diketomarcfortine D;

1-(p-toluenesulfonyl)-14,17-diketomarcfortine D;

1-acetyl-14,17-diketomarcfortine D;

1-methyl-14,17-diketomarcfortine D;

1-benzyl-14,17-diketomarcfortine D;

1-dimethylcarbamoyl-14,17-diketomarcfortine D;

1-methoxycarbonyl-14,17-diketomarcfortine D;

15,16-dehydro-14,17-diketomarcfortine A;

1-acetoxymethyl-15,16-dehydro-14,17-diketomarcfortine A;

1-diethoxyphosphoryl-15,16-dehydro-14,17-diketoxymarcfortine A;

1-dimethylsulfamoyl-15,16-dehydro-14,17-diketomarcfortine A;

1-cyclopropylcarbonyl-15,16-dehydro-14,17-diketomarcfortine A;

2-bicyclo 2.2.1!heptanoyl-15,16-dehydro-14,17-diketomarcfortine A;

1-(1-piperidinyl)thiocarbonyl-15,16-dehydro-14,17-diketomarcfortine A;

1-succinoyl-15,16-dehydro-14,17-diketomarcfortine A;

1-(4-morpholinosulfenyl)-15,16-dehydro-14,17-diketomarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-15,16-dehydro-14,17-diketomarcfortine A;

24-propoxy-24,25-dihydro-15,16-dehydro-14,17-diketomarcfortine A;

1-(p-toluenesulfonyl)-15,16-dehydro-14,17-diketomarcfortine A;

1-acetyl-15,16-dehydro-14,17-diketomarcfortine A;

1-methyl-15,16-dehydro-14,17-diketomarcfortine A;

1-benzyl-15,16-dehydro-14,17-diketomarcfortine A;

1-dimethylcarbamoyl-15,16-dehydro-14,17-diketomarcfortine A;

1-methoxycarbonyl-15,16-dehydro-14,17-diketomarcfortine A;

15,16-dehydro-14,17-diketomarcfortine B;

24,25-dihydro-15,16-dehydro-14,17-diketomarcfortine B;

24-methoxy-24,25-dihydro-15,16-dehydro-14,17-diketomarcfortine B;

1-(p-toluenesulfonyl)-15,16-dehydro-14,17-diketomarcfortine B;

1-ethyl-15,16-dehydro-14,17-diketomarcfortine B;

1-benzyl-15,16-dehydro-14,17-diketomarcfortine B;

18a-ethyl-15,16-dehydro-14,17-diketomarcfortine B;

18a-benzyl-15,16-dehydro-14,17-diketomarcfortine B;

18a-methoxyethoxymethyl-15,16-dehydro-14,17-diketomarcfortine B;

18a-allyl-15,16-dehydro-14,17-diketomarcfortine B;

18a-propargyl-15,16-dehydro-14,17-diketomarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-15,16-dehydro-14,17-diketomarcfortineB;

1,18a-bis-ethyl-15,16-dehydro-14,17-diketomarcfortine B;

1,18a-bis-benzyl-15,16-dehydro-14,17-diketomarcfortine B;

18a-ethyl-24-methoxy-15,16-dehydro-14,17-diketomarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxymarcfortine B;

18a-ethyl-24,25 dihydro-15,16-dehydro-14,17-diketomarcfortine B;

24,25 dihydro-15,16-dehydro-14,17-diketomarcfortine C;

1-(p-bromobenzene sulfonyl)-15,16-dehydro-14,17-diketomarcfortine C;

1-propionyl-15,16-dehydro-14,17-diketomarcfortine C;

1-propyl-15,16-dehydro-14,17-diketomarcfortine C;

1-benzyl-15,16-dehydro-14,17-diketomarcfortine C;

18a-propyl-15,16-dehydro-14,17-diketomarcfortine C;

18a-benzyl-15,16-dehydro-14,17-diketomarcfortine C;

18a-methoxyethoxymethyl-15,16-dehydro-14,17-diketomarcfortine C;

18-allyl-15,16-dehydro-14,17-diketomarcfortine C;

18a-propargyl-15,16-dehydro-14,17-diketomarcfortine C;

1,18a-bis-propyl-15,16-dehydro-14,17-diketomarcfortine C;

1,18a-bis-benzyl-15,16-dehydro-14,17-diketomarcfortine C;

15,16-dehydro-14,17-diketomarcfortine C;

1-(4-carbethoxy-1,3-thiazolidinin-3-yl)carbonyl-15,16-dehydro-14,17-diketomarcfortineA;

1-palmitoyl-15,16-dehydro-14,17-diketomarcfortine A;

1-(4-morpholinocarbonyl)-15,16-dehydro-14,17-diketomarcfortine A;

1-palmitoyl-15,16-dehydro-14,17-diketomarcfortine D;

1-(4-morpholinocarbonyl)-15,16-dehydro-14,17-diketomarcfortine D;

15,16-dehydro-14,17-diketomarcfortine D;

1-acetoxymethyl-15,16-dehydro-14,17-diketomarcfortine D;

1-diethoxyphosphoryl-15,16-dehydro-14,17-diketomarcfortine D;

1-dimethylsulfamoyl-15,16-dehydro-14,17-diketomarcfortine D;

1-cyclopropylcarbonyl-15,16-dehydro-14,17-diketomarcfortine D;

2-bicyclo 2.2.1!heptanoyl-15,16-dehydro-14,17-diketomarcfortine D;

1-(1-piperidinyl)thiocarbonyl-15,16-dehydro-14,17-diketomarcfortine D;

1-succinoyl-15,16-dehydro-14,17-diketomarcfortine D;

1-(4-morpholinosulfenyl)-15,16-dehydro-14,17-diketomarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-15,16-dehydro-14,17-diketomarcfortine D;

24-propoxy-24,25-dihydro-15,16-dehydro-14,17-diketomarcfortine D;

1-(p-toluenesulfonyl)-15,16-dehydro-14,17-diketomarcfortine D;

1-acetyl-15,16-dehydro-14,17-diketomarcfortine D;

1-methyl-15,16-dehydro-14,17-diketomarcfortine D;

1-benzyl-15,16-dehydro-14,17-diketomarcfortine D;

1-dimethylcarbamoyl-15,16-dehydro-14,17-diketomarcfortine D;

1-methoxycarbonyl-15,16-dehydro-14,17-diketomarcfortine D;

14α-hydroxy-14,3-methyl-17-ketomarcfortine A;

1-acetoxymethyl-14α-hydroxy- 14β-methyl-17-ketomarcfortine A;

1-diethoxyphosphoryl-14α-hydroxy-14β-methyl-17-ketoxymarcfortine A;

1-dimethylsulfamoyl-14α-hydroxy-14β-methyl-17-ketomarcfortine A;

1-cyclopropylcarbonyl-14α-hydroxy-14β-methyl-17-ketomarcfortine A;

2-bicyclo 2.2.1!heptanoyl-14α-hydroxy-14β-methyl-17-ketomarcfortine A;

1-(1-piperidinyl)thiocarbonyl-14α-hydroxy-14β-methyl-17-ketomarcfortineA;

1-succinoyl-14α-hydroxy-14β-methyl-17-ketomarcfortine A;

1-(4-morpholinosulfenyl)-14α-hydroxy-14β-methyl-17-ketomarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-14β-methyl-17-ketomarcfortineA;

24-propoxy-24,25-dihydro-14α-hydroxy-14β-methyl-17-ketomarcfortine A;

1-(p-toluenesulfonyl)-14α-hydroxy-14β-methyl-17-ketomarcfortine A;

1-acetyl-14α-hydroxy-14β-methyl-17-ketomarcfortine A;

1-methyl-14α-hydroxy-14β-methyl-17-ketomarcfortine A;

1-benzyl-14-hydroxy-14β-methyl-17-ketomarcfortine A;

1-dimethylcarbamoyl-14α-hydroxy-14β-methyl-17-ketomarcfortine A;

1-methoxycarbonyl-14α-hydroxy-14β-methyl-17-ketomarcfortine A;

14α-hydroxy-14β-methyl-17-ketomarcfortine B;

24,25-dihydro-14α-hydroxy-14β-methyl-17-ketomarcfortine B;

24-methoxy-24,25-dihydro-14α-hydroxy-14β-methyl-17-ketomarcfortine B;

1-(p-toluenesulfonyl)-14α-hydroxy-14β-methyl-17-ketomarcfortine B;

1-ethyl-14α-hydroxy-14,-methyl-17-ketomarcfortine B;

1-benzyl-14α-hydroxy-14β-methyl-17-ketomarcfortine B;

18a-ethyl-14α-hydroxy-14β-methyl-17-ketomarcfortine B;

18a-benzyl-14α-hydroxy-14β-methyl-17-ketomarcfortine B;

18a-methoxyethoxymethyl-14α-hydroxy-14β-methyl-17-ketomarcfortine B;

18a-allyl-14α-hydroxy-14β-methyl-17-ketomarcfortine B;

18a-propargyl-14α-hydroxy-14β-methyl-17-ketomarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxy-14β-methyl-17-ketomarcfortineB;

1,18a-bis-ethyl-14α-hydroxy-14β-methyl-17-ketomarcfortine B;

1,18a-bis-benzyl-14α-hydroxy-14β-methyl-17-ketomarcfortine B;

18a-ethyl-24-methoxy-14α-hydroxy-14β-methyl-17-ketomarcfortine B;

1-(2,4-dinitrobenzene sulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxymarcfortine B;

18a-ethyl-24,25 dihydro-14α-hydroxy-14β-methyl-17-ketomarcfortine B;

24,25 dihydro-14α-hydroxy-14β-methyl-17-ketomarcfortine C;

1-(p-bromobenzene sulfonyl)-14α-hydroxy-14β-methyl-17-ketomarcfortine C;

1-propionyl-14α-hydroxy-14β-methyl-17-ketomarcfortine C;

1-propyl-14α-hydroxy-14β-methyl-17-ketomarcfortine C;

1-benzyl-14α-hydroxy-14β-methyl-17-ketomarcfortine C;

18a-propyl-14α-hydroxy-14β-methyl-17-ketomarcfortine C;

18a-benzyl-14α-hydroxy-14β-methyl-17-ketomarcfortine C;

18a-methoxyethoxymethyl-14α-hydroxy-14β-methyl-17-ketomarcfortine C;

18-allyl-14α-hydroxy-14β-methyl-17-ketomarcfortine C;

18a-propargyl-14α-hydroxy-14β-methyl-17-ketomarcfortine C;

1,18a-bis-propyl-14α-hydroxy-14β-methyl-17-ketomarcfortine C;

1,18a-bis-benzyl-14α-hydroxy-14β-methyl-17-ketomarcfortine C;

14α-hydroxy-14β-methyl-17-ketomarcfortine C;

1-(4-carbethoxy-1,3-thiazolidinin-3-yl)carbonyl-14α-hydroxy-14β-methyl-17-ketomarcfortineA;

1-palmitoyl-14α-hydroxy-14β-methyl-17-ketomarcfortine A;

1-(4-morpholinocarbonyl)-14α-hydroxy-14β-methyl-17-ketomarcfortine A;

1-palmitoyl-14α-hydroxy-14β-methyl-17-ketomarcfortine D;

1-(4-morpholinocarbonyl)-14α-hydroxy-14β-methyl-17-ketomarcfortine D;

14α-hydroxy-14β-methyl-17-ketomarcfortine D;

1-acetoxymethyl-14α-hydroxy-14β-methyl-17-ketomarcfortine D;

1-diethoxyphosphoryl-14α-hydroxy-14β-methyl-17-ketomarcfortine D;

1-dimethylsulfamoyl-14α-hydroxy-14β-methyl-17-ketomarcfortine D;

1-cyclopropylcarbonyl-14α-hydroxy-14β-methyl-17-ketomarcfortine D;

2-bicyclo 2.2.1!heptanoyl-14α-hydroxy-14p-methyl-17-ketomarcfortine D;

1-(1-piperidinyl)thiocarbonyl-14α-hydroxy-14β-methyl-17-ketomarcfortineD;

1-succinoyl-14α-hydroxy-14β-methyl-17-ketomarcfortine D;

1-(4-morpholinosulfenyl)-14α-hydroxy-14β-methyl-17-ketomarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-14β-methyl-17-ketomarcfortineD;

24-propoxy-24,25-dihydro-14α-hydroxy-14β-methyl-17-ketomarcfortine D;

1-(p-toluenesulfonyl)-14α-hydroxy-14β-methyl-17-ketomarcfortine D;

1-acetyl-14α-hydroxy-14β-methyl-17-ketomarcfortine D;

1-methyl-14α-hydroxy-14β-methyl-17-ketomarefortine D;

1-benzyl-14α-hydroxy-14β-methyl-17-ketomarefortine D;

1-dimethylcarbamoyl-14α-hydroxy-14β-methyl-17-ketomarcfortine D;

1-methoxycarbonyl-14α-hydroxy-14β-methyl-17-ketomarcfortine D;

14-ketomarcfortine A;

1-acetoxymethyl-14-ketomarcfortine A;

1-diethoxyphosphoryl-14-ketoxymarcfortine A;

1-dimethylsulfamoyl-14-ketomarcfortine A;

1-cyclopropylcarbonyl-14-ketomarcfortine A;

2-bicyclo 2.2.1!heptanoyl-14-ketomarcfortine A;

1-(1-piperidinyl)thiocarbonyl-14-ketomarcfortine A;

1-succinoyl-14-ketomarcfortine A;

1-(4-morpholinosulfenyl)-14-ketomarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-14-ketomarcfortine A;

24-propoxy-24,25-dihydro-14-ketomarcfortine A;

1-(p-toluenesulfonyl)-14-ketomarcfortine A;

1-acetyl-14-ketomarcfortine A;

1-methyl-14-ketomarcfortine A;

1-benzyl-14-ketomarcfortine A;

1-dimethylcarbamoyl-14-ketomarcfortine A;

1-methoxycarbonyl-14-ketomarcfortine A;

14-ketomarcfortine B;

24,25-dihydro-14-ketomarcfortine B;

24-methoxy-24,25-dihydro-14-ketomarcfortine B;

1-(p-toluenesulfonyl)-14-ketomarcfortine B;

1-ethyl-14-ketomarcfortine B;

1-benzyl-14-ketomarcfortine B;

18a-ethyl-14-ketomarcfortine B;

18a-benzyl-14ketomarcfortine B;

18a-methoxyethoxymethyl-14-ketomarcfortine B;

18a-allyl-14ketomarcfortine B;

18a-propargyl-14-ketomarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-14-ketomarcfortine B;

1,18a-bis-ethyl-14-ketomarcfortine B;

1,18a-bis-benzyl-14-ketomarcfortine B;

18a-ethyl-24-methoxy-14-ketomarcfortine B;

1-(2,4-dinitrobenzene sulfonyl)-18α-ethyl-24-methoxy-24,25-dihydro-14α-hydroxymarcfortine B;

18a-ethyl-24,25 dihydro-14-ketomarcfortine B;

24,25 dihydro-14-ketomarcfortine C;

1-(p-bromobenzene sulfonyl)-14-ketomarcfortine C;

1-propionyl-14-ketomarcfortine C;

1-propyl-14-ketomarcfortine C;

1-benzyl-14-ketomarcfortine C;

18a-propyl-14-ketomarcfortine C;

18a-benzyl-14-ketomarcfortine C;

18a-methoxyethoxymethyl-14-ketomarcfortine C;

18-allyl-14-ketomarcfortine C;

18a-propargyl-14-ketomarcfortine C;

1,18a-bis-propyl-14-ketomarcfortine C;

1,18a-bis-benzyl-14-ketomarcfortine C;

14-ketomarcfortine C;

1-(4-carbethoxy-1,3-thiazolidinin-3-yl)carbonyl-14-ketomarcfortine A;

1-palmitoyl-14-ketomarcfortine A;

1-(4-morpholinocarbonyl)-14-ketomarcfortine A;

1-palmitoyl-14-ketomarcfortine D;

1-(4-morpholinocarbonyl)-14-ketomarcfortine D;

14-ketodroxymarcfortine D;

1-acetoxymethyl-14ketomarcfortine D;

1-diethoxyphosphoryl-14-ketomarcfortine D;

1-dimethylsulfamoyl-14ketomarcfortine D;

1-cyclopropylcarbonyl-14-ketomarcfortine D;

2-bicyclo 2.2.1!heptanoyl-14-ketomarcfortine D;

1-(1-piperidinyl)thiocarbonyl-14-ketomarcfortine D;

1-succinoyl-14-ketomarcfortine D;

1-(4-morpholinosulfenyl)-14ketomarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-14-ketomarcfortine D;

24-propoxy-24,25-dihydro-14-ketomarcfortine D;

1-(p-toluenesulfonyl)-14-ketomarcfortine D;

1-acetyl-14-ketomarcfortine D;

1-methyl-14-ketomarcfortine D;

1-benzyl-14-ketomarcfortine D;

1-dimethylcarbamoyl-14-ketomarcfortine D;

1-methoxycarbonyl-14-ketomarcfortine D;

16-dithio-17-ketomarcfortine A;

1-acetoxymethyl-16-dithio-17-ketomarcfortine A;

1-diethoxyphosphoryl-16-dithio-17-ketoxymarcfortine A;

1-dimethylsulfamoyl-16-dithio-17-ketomarcfortine A;

1-cyclopropylcarbonyl-16-dithio-17-ketomarcfortine A;

2-bicyclo 2.2.1!heptanoyl-16-dithio-17-ketomarcfortine A;

1-(1-piperidinyl)thiocarbonyl-16-dithio-17-ketomarcfortine A;

1-succinoyl-16-dithio-17-ketomarcfortine A;

1-(4-morpholinosulfenyl)-16-dithio-17-ketomarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-16-dithio-17-ketomarcfortine A;

24-propoxy-24,25-dihydro-16-dithio-17-ketomarcfortine A;

1-(p-toluenesulfonyl)-16-dithio-17-ketomarcfortine A;

1-acetyl-16-dithio-17-ketomarcfortine A;

1-methyl-16-dithio-17-ketomarcfortine A;

1-benzyl-16-dithio-17-ketomarcfortine A;

1-dimethylcarbamoyl-16-dithio-17-ketomarcfortine A;

1-methoxycarbonyl-16-dithio-17-ketomarcfortine A;

16-dithio-17-ketomarcfortine B;

24,25-dihydro-16-dithio-17-ketomarcfortine B;

24-methoxy-24,25-dihydro-16-dithio-17-ketomarcfortine B;

1-(p-toluenesulfonyl)-16-dithio-17-ketomarcfortine B;

1-ethyl-16-dithio-17-ketomarcfortine B;

1-benzyl-16-dithio-17-ketomarcfortine B;

18a-ethyl-16-dithio-17-ketomarcfortine B;

18a-benzyl-16-dithio-17-ketomarcfortine B;

18a-methoxyethoxymethyl-16-dithio-17-ketomarcfortine B;

18a-allyl-16-dithio-17-ketomarcfortine B;

18a-propargyl-16-dithio-17-ketomarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-16-dithio-17-ketomarcfortine B;

1,18a-bis-ethyl-16-dithio-17-ketomarcfortine B;

1,18a-bis-benzyl-16-dithio-17-ketomarcfortine B;

18a-ethyl-24-methoxy-16-dithio-17-ketomarcfortine B;

1-(2,4-dinitrobenzene sulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxymarcfortine B;

18a-ethyl-24,25 dihydro-16-dithio-17-ketomarcfortine B;

24,25 dihydro-16-dithio-17-ketomarcfortine C;

1-(p-bromobenzene sulfonyl)-16-dithio-17-ketomarcfortine C;

1-propionyl-16-dithio-17-ketomarcfortine C;

1-propyl-16-dithio-17-ketomarcfortine C;

1-benzyl-16-dithio-17-ketomarcfortine C;

18a-propyl-16-dithio-17-ketomarcfortine C;

18a-benzyl-16-dithio-17-ketomarcfortine C;

18a-methoxyethoxymethyl-16-dithio-17-ketomarcfortine C;

18-allyl-16-dithio-17-ketomarcfortine C;

18a-propargyl-16-dithio-17-ketomarcfortine C;

1,18a-bis-propyl-16-dithio-17-ketomarcfortine C;

1,18a-bis-benzyl-16-dithio-17-ketomarcfortine C;

16-dithio-17-ketomarcfortine C;

1-(4-carbethoxy-1,3-thiazolidinin-3-yl)carbonyl-16-dithio-17-ketomarcfortineA;

1-paliitoyl-16-dithio-17-ketomarcfortine A;

1-(4-morpholinocarbonyl)-16-dithio-17-ketomarcfortine A;

1-palmitoyl-16-dithio-17-ketomarcfortine D;

1-(4-morpholinocarbonyl)-16-dithio-17-ketomarcfortine D;

16-dithio-17-ketodroxymarcfortine D;

1-acetoxymethyl-16-dithio-17-ketomarcfortine D;

1-diethoxyphosphoryl-16-dithio-17-ketomarcfortine D;

1-dimethylsulfamoyl-16-dithio-17-ketomarcfortine D;

1-cyclopropylcarbonyl-16-dithio-17-ketomarcfortine D;

2-bicyclo 2.2.1!heptanoyl-16-dithio-17-ketomarcfortine D;

1-(1-piperidinyl)thiocarbonyl-16-dithio-17-ketomarcfortine D;

1-succinoyl-16-dithio-17-ketomarcfortine D;

1-(4-morpholinosulfenyl)-16-dithio-17-ketomarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-16-dithio-17-ketomarcfortine D;

24-propoxy-24,25-dihydro-16-dithio-17-ketomarcfortine D;

1-(p-toluenesulfonyl)-16-dithio-17-ketomarcfortine D;

1-acetyl-16-dithio-17-ketomarcfortine D;

1-methyl-16-dithio-17-ketomarcfortine D;

1-benzyl-16-dithio-17-ketomarcfortine D;

1-dimethylcarbarnoyl-16-dithio-17-ketomarcfortine D; or

1-methoxycarbonyl-16-dithio-17-ketomarcfortine D.

16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;

1-acetoxymethyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;

1-diethoxyphosphoryl-16-thiophenyl-15,16-dehydro-17-ketoxymarcfortine A;

1-dimethylsulfamoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;

1-cyclopropylcarbonyl-16-thiophenyl-15,16-dehydro-17-ketomarcfordne A;

2-bicyclo 2.2.1!heptanoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortineA;

1-(1-piperidinyl)thiocarbonyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortineA;

1-succinoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;

1-(4-morpholinosulfenyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortineA;

1-(2,4-dinitrobenzenesulfenyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortineA;

24-propoxy-24,25-dihydro-16-thiophenyl-15,16-dehydro-17-ketomarcfortineA;

1-(p-toluenesulfonyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;

1-acetyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;

1-methyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;

1-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;

1-dimethylcarbamoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;

1-methoxycarbonyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;

16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

24,25-dihydro-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

24-methoxy-24,25-dihydro-16-thiophenyl-15,16-dehydro-17-ketomarcfortineB;

1-(p-toluenesulfonyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

1-ethyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

1-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

18a-ethyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

18a-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

18a-methoxyethoxymethyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortineB;

18a-allyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

18a-propargyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-16-thiophenyl-15,16-dehydro-17-ketomarcfortineB;

1,18a-bis-ethyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

1,18a-bis-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

18a-ethyl-24-methoxy-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxymarcfortine B;

18a-ethyl-24,25 dihydro-16-thiophenyl-15,16-dehydro-17-ketomarcfortineB;

24,25 dihydro-16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

1-(p-bromobenzenesulfonyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

1-propionyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

1-propyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

1-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

18a-propyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

18a-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

18a-methoxyethoxymethyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortineC;

18-allyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

18a-propargyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

1,18a-bis-propyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

1,18a-bis-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

1-(4-carbethoxy-1,3-thiazolidinin-3-yl)carbonyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortineA;

1-palmitoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;

1-(4-morpholinocarbonyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortineA.;

1-palmitoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D;

1-(4-morpholinocarbonyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortineD;

16-thiophenyl-15,16-dehydro-17-ketodroxymarcfortine D;

1-acetoxymethyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D;

1-diethoxyphosphoryl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D;

1-dimethylsulfamoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D;

1-cyclopropylcarbonyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D;

2-bicyclo 2.2.1!heptanoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortineD;

1-(1-piperidinyl)thiocarbonyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortineD;

1-succinoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D;

1-(4-morpholinosulfenyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortineD;

1-(2,4-dinitrobenzenesulfenyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortineD;

24-propoxy-24,25-dihydro-16-thiophenyl-15,16-dehydro-17-ketomarcfortineD;

1-(p-toluenesulfonyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D;

1-acetyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D;

1-methyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D;

1-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D;

1-dimethylcarbamoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D; or

1-methoxycarbonyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D.

16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;

1-acetoxymethyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;

1-diethoxyphosphoryl-16-thiophenyl-15,16-dehydro-17-ketoxymarcfortine A;

1-dimethylsulfamoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;

1-cyclopropylcarbonyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;

2-bicyclo 2.2.1!heptanoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortineA,;

1-(1-piperidinyl)thiocarbonyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortineA;

1-succinoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;

1-(4morpholinosulfenyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortineA;

1-(2,4-dinitrobenzenesulfenyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortineA;

24-propoxy-24,25-dihydro-16-thiophenyl-15,16-dehydro-17-ketomarcfortineA;

1-(p-toluenesulfonyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;

1-acetyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;

1-methyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;

1-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;

1-dimethylcarbamoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;

1-methoxycarbonyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;

16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

24,25-dihydro-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

24-methoxy-24,25-dihydro-16-thiophenyl-15,16-dehydro-17-ketomarcfortineB;

1-(p-toluenesulfonyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

1-ethyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

1-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

18a-ethyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

18a-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

18a-methoxyethoxymethyl-16-thiophenyl-15, 16-dehydro-17-ketomarcfortineB;

18a-allyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

18a-propargyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-16-thiophenyl-15,16-dehydro-17-ketomarcfortineB;

1,18a-bis-ethyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

1,18a-bis-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

18a-ethyl-24-methoxy-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxymarcfortine B;

18a-ethyl-24,25 dihydro-16-thiophenyl-15,16-dehydro-17-ketomarcfortineB;

24,25 dihydro-16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

1-(p-bromobenzenesulfonyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

1-propionyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

1-propyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

1-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

18a-propyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

18a-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

18a-methoxyethoxymethyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortineC;

18-allyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

18a-propargyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

1,18a-bis-propyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

1,18a-bis-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

16-thiophenyl-15,16-dehydro-17-ketomarcfortine C;

1-(4-carbethoxy-1,3-thiazolidinin-3-yl)carbonyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortineA;

1-palmitoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;

1-(4-morpholinocarbonyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortineA;

1-palmitoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D;

1-(4-morpholinocarbonyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortineD;

16-thiophenyl-15,16-dehydro-17-ketodroxymarcfortine D;

1-acetoxymethyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D;

1-diethoxyphosphoryl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D;

1-dimethylsulfamoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D;

1-cyclopropylcarbonyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D;

2-bicyclo 2.2.1!heptanoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortineD,

1-(1-piperidinyl)thiocarbonyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortineD;

1-succinoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D;

1-(4-morpholinosulfenyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortineD;

1-(2,4-dinitrobenzenesulfenyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortineD;

24-propoxy-24,25-dihydro-16-thiophenyl-15,16-dehydro-17-ketomarcfortineD;

1-(p-toluenesulfonyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D;

1-acetyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D;

1-methyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D;

1-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D;

1-dimethylcarbamoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D; or

1-methoxycarbonyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine D.

14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine A;

1-acetoxymethyl-14α-hydroxy-141-methyl-15-methyl-17-ketomarcfortine A;

1-diethoxyphosphoryl-14α-hydroxy-14β-methyl-15α-methyl-17-ketoxymarcfortineA;

1-dimethylsulfamoyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortiineA;

1-cyclopropylcarbonyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineA;

2-bicyclo2.2.1!heptanoyl-14α-hydroxy-141-methyl-15α-methyl-17-ketomarcfortine A;

1-(1-piperidinyl)thiocarbonyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineA;

1-succinoyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine A;

1-(4-morpholinosulfenyl)-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineA;

1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineA;

24-propoxy-24,25-dihydro-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineA;

1-(p-toluenesulfonyl)-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineA;

1-acetyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine A;

1-methyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine A;

1-benzyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine A;

1-dimethylcarbamoyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineA;

1-methoxycarbonyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineA;

14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine B;

24,25-dihydro-14(α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine B;

24-methoxy-24,25-dihydro-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineB;

1-(p-toluenesulfonyl)-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineB;

1-ethyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine B;

1-benzyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine B;

18a-ethyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine B;

18a-benzyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine B;

18a-methoxyethoxymethyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineB;

18a-allyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine B;

18a-propargyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxy-14β-methyl-15.alpha.-methyl-17-ketomarcfortineB;

1,18a-bis-ethyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine B;

1,18a-bis-benzyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine B;

18a-ethyl-24-methoxy-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineB;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxymarcfortine B;

18a-ethyl-24,25 dihydro-14α-hydroxy-14β-methyl-1Sa-methyl-17-ketomarcfortine B;

24,25 dihydro-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine C;

1-(p-bromobenzenesulfonyl)-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine C;

1-propionyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine C;

1-propyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine C;

1-benzyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine C;

18a-propyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine C;

18a-benzyl-14α-hydroxy-1β,-methyl-15α-methyl-17-ketomarcfortine C;

18a-methoxyethoxymethyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomar-fortineC;

18-allyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine C;

18a-propargyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine C;

1,18a-bis-propyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine C:

1,18a-bis-benzyl-14c-hydroxy-140-methyl-15a-methyl-17-ketomarcfortine C.

14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine C;

1-(4-carbethoxy-1,3-thiazolidinin-3-yl)carbonyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineA;

1-palmitoyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine A;

1-(4-morpholinocarbonyl)-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineA;

1-palmitoyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine D;

1-(4-morpholinocarbonyl)-14α-hydroxy-14β-methyl-15α-methyl-7-ketomarcfortineD;

14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine D;

1-acetoxymethyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine D;

1-diethoxyphosphoryl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineD;

1-dimethylsulfamoyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineD;

1-cyclopropylcarbonyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineD;

2-bicyclo2.2.1!heptanoyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine D;

1-(1-piperidinyl)thiocarbonyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineD;

1-succinoyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine D;

1-(4-morpholinosulfenyl)-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineD;

1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineD;

24-propoxy-24,25-dihydro-14α-hydroxy-14β-methyl-15α-methy1-17-ketomacfortineD;

1-(p-toluenesulfonyl)-14α-hydroxy-14β-methyl-15a-methyl-17-ketomarcfortine D;

1-acetyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine D;

1-methyl-14α-hydroxy-14β-methyl-5α-methyl-17-ketomarcfortine D;

1-benzyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine D;

1-dimethylcarbamoyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineD;

1-methoxycarbonyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineD;

14α-hydroxy-15α-methyl-17-ketomarcfortine A;

1-acetoxymethyl-14α-hydroxy-15α-methyl-17-ketomarcfortine A;

1-diethoxyphosphoryl-14α-hydroxy-15α-methyl-17-ketoxymarcfortine A;

1-dimethylsulfamoyl-14α-hydroxy-15α-methyl-17-ketomarcfortine A;

1-cyclopropylcarbonyl-14α-hydroxy-15α-methyl-17-ketomarcfortine A;

2-bicyclo 2.2.1!heptanoyl-14α-hydroxy-15α-methyl-17-ketomarcfortine A;

1-(1-piperidinyl)thiocarbonyl-14α-hydroxy-15α-methyl-17-ketomarcfortineA;

1-succinoyl-14α-hydroxy-15α-methyl-17-ketomarcfortine A;

1-(4-morpholinosulfenyl)-14α-hydroxy-15α-methyl-17-ketomarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-15α-methyl-17-ketomarcfortineA;

24-propoxy-24,25-dihydro-14α-hydroxy-15α-methyl-17-ketomarcfortine A;

1-(p-toluenesulfonyl)-14α-hydroxy-15α-methyl-17-ketomarcfortine A;

1-acetyl-14α-hydroxy-15α-methyl-17-ketomarcfortine A;

1-methyl-14α-hydroxy-15α-methyl-17-ketomarcfortine A;

1-benzyl-14α-hydroxy-15α-methyl-17-ketomarcfortine A;

1-dimethylcarbamoyl-14α-hydroxy-15α-methyl-17-ketomarcfortine A;

1-methoxycarbonyl-14α-hydroxy-15α-methyl-17-ketomarcfortine A;

14α-hydroxy-15α-methyl-17-ketomarcfortine B;

24,25-dihydro-14α-hydroxy-15α-methyl-17-ketomarcfortine B;

24-methoxy-24,25-dihydro-14α-hydroxy-15α-methyl-17-ketomarcfortine B;

1-(p-toluenesulfonyl)-14α-hydroxy-15α-methyl-17-ketomarcfortine B;

1-ethyl-14α-hydroxy-15α-methyl-17-ketomarcfortine B;

1-benzyl-14α-hydroxy-15α-methyl-17-ketomarcfortine B;

18a-ethyl-14α-hydroxy-15α-methyl-17-ketomarcfortine B;

18a-benzyl-14α-hydroxy-15α-methyl-17-ketomarcfortine B;

18a-methoxyethoxymethyl-14α-hydroxy-15α-methyl-17-ketomarcfortine B;

18a-allyl-14α-hydroxy-15α-methyl-17-ketomarcfortine B;

18a-propargyl-14α-hydroxy-15α-methyl-17-ketomarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxy-15α-methyl-17-ketomarcfortineB;

1,18a-bis-ethyl-14α-hydroxy-15α-methyl-17-ketomarcfortine B;

1,18a-bis-benzyl-14α-hydroxy-15α-methyl-17-ketomarcfortine B;

18a-ethyl-24-methoxy-14α-hydroxy-15α-methyl-17-ketomarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxymarcfortine B;

18a-ethyl-24,25-dihydro-14α-hydroxy-15α-methyl-17-ketomarcfortine B;

24,25 dihydro-14α-hydroxy-15α-methyl-17-ketomarcfortine C;

1-(p-bromobenzene sulfonyl)-14α-hydroxy-15α-methyl-17-ketomarcfortine C;

1-propionyl-14α-hydroxy-15α-methyl-17-ketomarcfortine C;

1-propyl-14α-hydroxy-15α-methyl-17-ketomarcfortine C;

1-benzyl-14α-hydroxy-15α-methyl-17-ketomarcfortine C;

18a-propyl-14α-hydroxy-15α-methyl-17-ketomarcfortine C;

18a-benzyl-14α-hydroxy-15α-methyl-17-ketomarcfortine C;

18a-methoxyethoxymethyl-14α-hydroxy-15α-methyl-17-ketomarcfortine C;

18-allyl-14α-hydroxy-15α-methyl-17-ketomarcfortine C;

18a-propargyl-14α-hydroxy-15α-methyl-17-ketomarcfortine C;

1,18a-bis-propyl-14α-hydroxy-15α-methyl-17-ketomarcfortine C;

1,18a-bis-benzyl-14α-hydroxy-15α-methyl-17-ketomarcfortine C;

14α-hydroxy-15α-methyl-17-ketomarcfortine C;

1-(4-carbethoxy-1,3-thiazolidinin-3-yl)carbonyl-14α-hydroxy-15α-methyl-17-ketomarcfortineA;

1-palmitoyl-14α-hydroxy-15α-methyl-17-ketomarcfortine A;

1-(4-morpholinocarbonyl)-14α-hydroxy-15α-methyl-17-ketomarcfortine A;

1-palmitoyl-14α-hydroxy-15α-methyl-17-ketomarcfortine D;

1-(4-morpholinocarbonyl)-14α-hydroxy-15α-methyl-17-ketomarcfortine D;

14α-hydroxy-15α-methyl-17-ketomarcfortine D;

1-acetoxymethyl-14α-hydroxy-15α-methyl-17-ketomarcfortine D;

1-diethoxyphosphoryl-14α-hydroxy-15α-methyl-17-ketomarcfortine D;

1-dimethylsulfamoyl-14α-hydroxy-15α-methyl-17-ketomarcfortine D;

1-cyclopropylcarbonyl-14α-hydroxy-15α-methyl-17-ketomarcfortine D;

2-bicyclo 2.2.1!heptanoyl-14α-hydroxy-15α-methyl-17-ketomarcfortine D;

1-(1-piperidinyl)thiocarbonyl-14α-hydroxy-15α-methyl-17-ketomarcfortineD;

1-succinoyl-14α-hydroxy-15α-methyl-17-ketomarcfortine D;

1-(4-morpholinosulfenyl)-14α-hydroxy-15α-methyl-17-ketomarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-15α-methyl-17-ketomarcfortineD;

24-propoxy-24,25-dihydro-14α-hydroxy-15α-methyl-17-ketomarcfortine D;

1-(p-toluenesulfonyl)-14α-hydroxy-15α-methyl-17-ketomarcfortine D;

1-acetyl-14α-hydroxy-15α-methyl-17-ketomarcfortine D;

1-methyl-14α-hydroxy-15α-methyl-17-ketomarcfortine D;

1-benzyl-14α-hydroxy-15α-methyl-17-ketomarcfortine D;

1-dimethylcarbamoyl-14α-hydroxy-15α-methyl-17-ketomarcfortine D;

1-methoxycarbonyl-14α-hydroxy-15α-methyl-17-ketomarcfortine D;

15α-methyl-14,17-diketomarcfortine A;

1-acetoxymethyl-15α-methyl-14,17-diketomarcfortine A;

1-diethoxyphosphoryl-15α-methyl-14,17-diketoxymarcfortine A;

1-dimethylsulfamoyl-15α-methyl-14,17-diketomarcfortine A;

1-cyclopropylcarbonyl-15α-methyl-14,17-diketomarcfortine A;

2-bicyclo 2.2.1!heptanoyl-15α-methyl-14,17-diketomarcfortine A;

1-(1-piperidinyl)thiocarbonyl-15α-methyl-14,17-diketomarcfortine A;

1-succinoyl-15α-methyl-14,17-diketomarcfortine A;

1-(4-morpholinosulfenyl)-15α-methyl-14,17-diketomarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-15α-methyl-14,17-diketomarcfortine A;

24-propoxy-24,25-dihydro-15 -methyl-14,17-diketomarcfortine A;

1-(p-toluenesulfonyl)-15α-methyl-14,17-diketomarcfortine A;

1-acetyl-15α-methyl-14,17-diketomarcfortine A;

1-methyl-15α-methyl-14,17-diketomarcfortine A;

1-benzyl-15α-methyl-14,17-diketomarcfortine A;

1-dimethylcarbamoyl-15α-methyl-14,17-diketomarcfortine A;

1-methoxycarbonyl-15α-methyl-14,17-diketomarcfortine A;

15α-methyl-14,17-diketomarcfortine B;

24,25-dihydro-15α-methyl-14,17-diketomarcfortine B;

24-methoxy-24,25-dihydro-15α-methyl-14,17-diketomarcfortine B;

1-(p-toluenesulfonyl)-15α-methyl-14,17-diketomarofortine B;

1-ethyl-15α-methyl-14,17-diketomarcfortine B;

1-benzyl-15α-methyl-14,17-diketomarcfortine B;

18a-ethyl-15α-methyl-14,17-diketomarcfortine B;

18a-benzyl-15α-methyl-14,17-diketomarcfortine B;

18a-methoxyethoxymethyl-15α-methyl-14,17-diketomarcfortine B;

18a-allyl-15α-methyl-14,17-diketomarcfortine B;

18a-propargyl-15α-methyl-14,17-diketomarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-15α-methyl-14,17-diketomarcfortine E;

1,18a-bis-ethyl-15α-methyl-14,17-diketomarcfortine B;

1,18a-bis-benzyl-15α-methyl-14,17-diketomarcfortine B;

18a-ethyl-24-methoxy-15α-methyl-14,17-diketomarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxymarcfortine B;

18a-ethyl-24,25-dihydro-15α-methyl-14,17-diketomarcfortine B;

24,25 dihydro-15α-methyl-14,17-diketomarcfortine C;

1-(p-bromobenzene sulfonyl)-15α-methyl-14,17-diketomarcfortine C;

1-propionyl-15α-methyl-14,17-diketomarcfortine C;

1-propyl-15α-methyl-14,17-diketomarcfortine C;

1-benzyl-15α-methyl-14,17-diketomarcfortine C;

18a-propyl-15α-methyl-14,17-diketomarcfortine C;

18a-benzyl-15α-methyl-14,17-diketomarcfortine C;

18a-methoxyethoxymethyl-15α-methyl-14,17-diketomarcfortine C;

18-allyl-15α-methyl-14,17-diketomarcfortine C;

18a-propargyl-15α-methyl-14,17-diketomarcfortine C;

1,18a-bis-propyl-15α-methyl-14,17-diketomarcfortine C;

1,18a-bis-benzyl-15α-methyl-14,17-diketomarcfortine C;

15α-methyl-14,17-diketomarcfortine C;

1-(4-carbethoxy-1,3-thiazolidinin-3-yl)carbonyl-15α-methyl-14,17-diketomarcfortineA;

1-palmitoyl-15α-methyl-14,17-diketomarcfortine A;

1-(4-morpholinocarbonyl)-15α-methyl-14,17-diketomarcfortine A;

1-palmitoyl-15α-methyl-14,17-diketomarcfortine D;

1-(4-morpholinocarbonyl)-15α-methyl-14,17-diketomarcfortine D;

15α-methyl-14,17-diketomarcfortine D;

1-acetoxymethyl-15α-methyl-14,17-diketomarcfortine D;

1-diethoxyphosphoryl-15α-methyl-14,17-diketomarcfortine D;

1-dimethylsulfamoyl-15α-methyl-14,17-diketomarcfortine D;

1-cyclopropylcarbonyl-15α-methyl-14,17-diketomarcfortine D;

2-bicyclo 2.2.1!heptanoyl-15α-methyl-14,17-diketomarcfortine D;

1-(1-piperidinyl)thiocarbonyl-15α-methyl-14,17-diketomarcfortine D;

1-succinoyl-15α-methyl-14,17-diketomarcfortine D;

1-(4-morpholinosulfenyl)-15α-methyl-14,17-diketomarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-15α-methyl-14,17-diketomarcfortine D;

24-propoxy-24,25-dihydro-15α-methyl-14,17-diketomarcfortine D;

1-(p-toluenesulfonyl)-15α-methyl-14,17-diketomarcfortine D;

1-acetyl-15α-methyl-14,17-diketomarcfortine D;

1-methyl-15α-methyl-14,17-diketomarcfortine D;

1-benzyl-15α-methyl-14,17-diketomarcfortine D;

1-dimethylcarbamoyl-15α-methyl-14,17-diketomarcfortine D;

1-methoxycarbonyl-15α-methyl-14,17-diketomarcfortine D;

14,15-dehydro-16,17-diketomarcfortine A;

1-acetoxymethyl-14,15-dehydro-16,17-diketomarcfortine A;

1-diethoxyphosphoryl-14,15-dehydro-16,17-diketoxymarcfortine A;

1-dimethylsulfamoyl-14,15-dehydro-16,17-diketomarcfortine A;

1-cyclopropylcarbonyl-14,15-dehydro-16,17-diketomarcfortine A;

2-bicyclo 2.2.1!heptanoyl-14,15-dehydro-16,17-diketomarcfortine A;

1-(l-piperidinyl)thiocarbonyl-14,15-dehydro-16,17-diketomarcfortine A;

1-succinoyl-14,15-dehydro-16,17-diketomarcfortine A;

1-(4-morpholinosulfenyl)-14,15-dehydro-16,17-diketomarcfortine A;

1-(2,4-dinitrobenzenesulfenyl)-14,15-dehydro-16,17-diketomarcfortine A;

24-propoxy-24,25-dihydro-14,15-dehydro-16,17-diketomarcfortine A;

1-(p-toluenesulfonyl)-14,15-dehydro-16,17-diketomarcfortine A;

1-acetyl-14,15-dehydro-16,17-diketomarcfortine A;

1-methyl-14,15-dehydro-16,17-diketomarcfortine A;

1-benzyl-14,15-dehydro-16,17-diketomarcfortine A;

1-dimethylcarbamoyl-14,15-dehydro-16,17-diketomarcfortine A;

1-methoxycarbonyl-14,15-dehydro-16,17-diketomarcfortine A;

14,15-dehydro-16,17-diketomarcfortine B;

24,25-dihydro-14,15-dehydro-16,17-diketomarcfortine B;

24-methoxy-24,25-dihydro-14,15-dehydro-16,17-diketomarcfortine B;

1-(p-toluenesulfonyl)-14,15-dehydro-16,17-diketomarcfortine B;

1-ethyl-14,15-dehydro-16,17-diketomarcfortine B;

1-benzyl-14,15-dehydro-16,17-diketomarcfortine B;

18a-ethyl-14,15-dehydro-16,17-diketomarcfortine B;

18a-benzyl-14,15-dehydro-16,17-diketomarcfortine B;

18a-methoxyethoxymethyl-14,15-dehydro-16,17-diketomarcfortine B;

18a-allyl-14,15-dehydro-16,17-diketomarcfortine B;

18a-propargyl-14,15-dehydro-16,17-diketomarcfortine B;

18a-ethyl-24-methoxy-24,25-dihydro-14,15-dehydro-16,17-diketomarcfortineE,;

1,18a-bis-ethyl-14,15-dehydro-16,17-diketomarcfortine B;

1,18a-bis-benzyl-14,15-dehydro-16,17-diketomarcfortine B;

18a-ethyl-24-methoxy-14,15-dehydro-16,17-diketomarcfortine B;

1-(2,4-dinitrobenzenesulfonyl)-18a-ethyl-24-methoxy-24,25-dihydro-14α-hydroxymarcfortine B;

18a-ethyl-24,25 dihydro-14,15-dehydro-16,17-diketomarcfortine B;

24,25 dihydro-14,15-dehydro-16,17-diketomarcfortine C;

1-(p-bromobenzene sulfonyl)-14,15-dehydro-16,17-diketomarcfortine C;

1-propionyl-14,15-dehydro-16,17-diketomarcfortine C;

1-propyl-14,15-dehydro-16,17-diketomarcfortine C;

1-benzyl-14,15-dehydro-16,17-diketomarcfortine C;

18a-propyl-14,15-dehydro-16,17-diketomarcfortine C;

18a-benzyl-14,15-dehydro-16,17-diketomarcfortine C;

18a-methoxyethoxymethyl-14,15-dehydro-16,17-diketornarcfortine C;

18-allyl-14,15-dehydro-16,17-diketomarcfortine C;

18a-propargyl-14,15-dehydro-16,17-diketomarcfortine C;

1,18a-bis-propyl-14,15-dehydro-16,17-diketomarcfortine C;

1,18a-bis-benzyl-14,15-dehydro-16,17-diketomarcfortine C;

14,15-dehydro-16,17-diketomarcfortine C;

1-(4-carbethoxy-1,3-thiazolidinin-3-yl)carbonyl-14,15-dehydro-16,17-diketomarcfortineA;

1-palmitoyl-14,15-dehydro-16,17-diketomarcfortine A;

1-(4-morpholinocarbonyl)-14,15-dehydro-16,17-diketomarcfortine A;

1-palmitoyl-14,15-dehydro-16,17-diketomarcfortine D;

1-(4-morpholinocarbonyl)-14,15-dehydro-16,17-diketomarcfortine D;

14,15-dehydro-16,17-diketomarcfortine D;

1-acetoxymethyl-14,15-dehydro-16,17-diketomarcfortine D;

1-diethoxyphosphoryl-14,15-dehydro-16,17-diketomarcfortine D;

1-dimethylsulfamoyl-14,15-dehydro-16,17-diketomarcfortine D;

1-cyclopropylcarbonyl-14,15-dehydro-16,17-diketomarcfortine D;

2-bicyclo 2.2.1!heptanoyl-14,15-dehydro-16,17-diketomarcfortine D;

1-(1-piperidinyl)thiocarbonyl-14,15-dehydro-16,17-diketomarcfortine D;

1-succinoyl-14,15-dehydro-16,17-diketomarcfortine D;

1-(4-morpholinosulfenyl)-14,15-dehydro-16,17-diketomarcfortine D;

1-(2,4-dinitrobenzenesulfenyl)-14,15-dehydro-16,17-diketomarcfortine D;

24-propoxy-24,25-dihydro-14,15-dehydro-16,17-diketomarcfortine D;

1-(p-toluenesulfonyl)-14,15-dehydro-16,17-diketomarcfortine D;

1-acetyl-14,15-dehydro-16,17-diketomarcfortine D;

1-methyl-14,15-dehydro-16,17-diketomarcfortine D;

1-benzyl-14,15-dehydro-16,17-diketomarcfortine D;

1-dimethylcarbamoyl-14,15-dehydro-16,17-diketomarcfortine D; and

1-methoxycarbonyl-14,15-dehydro-16,17-diketomarcfortine D.

General procedures for the preparation of heteroaromatic N-oxides can befound in Chapter II of "Chemistry of the Heterocyclic N-Oxides", A. R.Katritzky and J. M. Lagowski, published 1971 Academic Press (Vol. 19 ofORGANIC CHEMISTRY--A Series of Monographs). Typically the N-oxide isformed by reaction with a percarboxylic acid in an appropriate solvent.Most suitably an aromatic peracid in a non-polar solvent is used, sincethe reaction may usually be carried out at room temperature. Suitablearomatic peracids include perbenzoic acid, chloroperbenzoic acid andperphthalic acid.

PREPARATION OF STARTING MATERIAL

N-18a substituted marcfortines B and C and C24-C25 modified marcfortinesare readily prepared by procedures given in U.S. Pat. No. 4,923,867, thedisclosure of which is incorporated herein by reference.

Marcfortines A, B and C are isolated, along with the previously knownroquefortine, as fungal metabolites of Penicillium roqueforti usingstandard fermentation and isolation techniques. The isolation, as wellas the analytical and structural characteristics of marcfortine A, aredescribed in detail in Polonsky et al Journal of the Chemical SocietyChemical Communications 1980, 601-602. The isolation, as well as theanalytical and structural characteristics of marcfortines B and C, aredescribed in detail in Polonsky et al Tetrahedron Letters 1981, 22,1977-1980.

Alternatively, and more preferably, Marcfortines A, C, and D may beisolated from Penicillium sp. UC7780 (strain number in Upjohn CultureCollection, UC 7780, The Upjohn Company, Kalamazoo, Mich.). This strainwas isolated from a soil sample collected in Illinois, deposited in theU.S. Department of Agriculture patent culture collection in Peoria, Ill.and given the accession number NRRL 18887. To further characterize thefungus a taxonomy study was done following the methods and materialsdescribed by I. John Pitt, The Genus Penicillium, Academic Press,London, (1979). Spore and hyphae surfaces were examined by scanningelectron microscopy according to the methods of Dietz, A. and Matthews,J, Appl. Microbiology 18:694-696 (1969). Intact conidiophores arevisualized by light microscopy A. H. S. Onions et al., Smith'sIntroduction to Industrial Mycology, John Wiley and Sons, New York, pp301-302 (1979)! after slide culture(s) are prepared: A glass petri dishcontaining glass beads, microscope slide, and coverslip are sterilized.A small block of potato dextrose agar is placed on the slide andinoculated on four sides with the fungus culture. The coverslip is seton the inoculated agar block and sterile water added to maintainmoisture. The chamber is incubated for six days at 24° C. A slide isprepared by removing the coverslip and placing it on a drop oflactophenol cotton blue stain.

The characteristics of Penicillium sp. UC 7780 (NRRL 18887) are asfollows:

Morphology--a biverticillate penicillus (two branch points betweenconidium and stipe). These branches (metulae) support the phialides orconidia bearing structures. Conidiophores (approximately 35 μm)terminated in verticils of 2-5 (10-14 μm) metulae. Phialides wereampulliform (like an ancient Greek wine jar) in verticils of 2-5 (7 μm).Conidia were smooth and spheroidal (2 μm) typically appearing in longcolumns. The stipe walls were smooth.

The culture was inoculated onto three petri dishes of Czapek yeast agar(CYA), one being 6 cm in diameter and one each of malt extract agar(MEA) and 25% glycerol nitrate agar (G25N). Inoculation was made from asemisolid suspension (0.5 ml of 0.2% agar with 0.05% Tween 80). Aninoculating loop of conidia was added to the tube and mixed. A loop ofsuspension was inoculated in a pattern of three sites per plate. Aneedle was used to stab inoculate the 6 cm plate. The incubation regimewas: one CYA plate plus the MEA and G25N plates at 24° C., one CYA plateat 37° C., and the 6 cm CYA plate at 5° C. After seven days the colonydiameters, colors, and other characters were recorded and are set forthin Table I. On potato dextrose agar (PDA, Difco), a deep red color onthe bottom or reverse of the colony is produced.

No sexual stage was noted. This results in the culture (NRRL 18887)being keyed in the Penicillium Key to subgenera. Within the PenicilliumKey, the penicillus type alone determines the subgenus to which aspecies is allocated. This species has several characteristics thatdistinguish it from the Biverticillium subgenus even though itspenicillus is biverticilliate. The species consistently producescolonies greater than 10 mm in diameter in 7 days on glycerol nitrateagar. The metulae appear longer than the phialides and are in verticilsof 2-5. These characteristics place this Penicillium sp. (NRRL 18887)into the subgenus Furcatum.

The foregoing description is illustrative of a strain of Penicillium sp.UC 7780 (NRRL 18887) which can be employed in the production ofMarcfortine and derivatives thereof. However, the present invention alsoembraces mutants of the above described microorganism. For example,those mutants which are obtained by natural selection or those producedby mutating agents including ionizing radiation such as ultravioletirradiation, or chemical mutagens such as nitrosoguanidine or the liketreatments are also included within the ambit of this invention.

This description is also desired and intended to include inter- andintraspecific genetic recombinants produced by genetic techniques wellknown to those skilled in the art, such as, for example, conjugation,transultion and genetic engineering techniques.

Penicillium sp. UC 7780 (NRRL 18887) may be cultivated under aerobiccondition in the same manner as commonly employed in the art forcultivation of a known strain of the genus Penicillium.

As medium components may be employed any of the well-known nutrientmaterials for Penicillium. For instance, as an assimilable carbonsource, glucose, glycerol, maltose, dextrin, starch, lactose, sucrose,molasses, soybean oil, cotton seed oil, etc., preferably glucose andglycerol may be employed and, as an assimilable nitrogen source, soybeanmeal, peanut meal, cotton seed meal, fish meal, corn steep liquor,peptone, rice, bran, meat extract, yeast, yeast extract, sodium nitrate,ammonium nitrate, ammonium sulfate, etc. may be used. And, suchinorganic salts as sodium chloride, phosphates, calcium carbonate, etc.may be added to a culture medium. A minor amount of a metal salt mayalso be added, if necessary. Further, a minor amount of a heavy metalmay be added, if necessary.

Particularly, in cultivating the Penicillium sp. (NRRL 18887) underaerobic condition, ordinary aerobic cultivation methods such as, forexample, solid culture, culture under aeration and agitation, shakenculture etc. may be favorably utilized.

In carrying out cultivation with aeration and agitation, an anti-foamingagent, e.g., silicon oil, vegetable oils, surfactants, etc. may besuitably employed.

The pH of the medium may be usually within a pH range of 3-9 andpreferably within or around neutral range and cultivation temperaturesmay be usually of 20°-30° C., in particular about 21° C. beingpreferred.

Cultivation may be continued until Marcfortine A will be substantiallyaccumulated in a culture medium, usually for 20 hours to 240 hours,preferably for 48 hours to 168 hours and, after cultivation, MarcfortineA may be isolated and recovered from a cultured broth by a suitablecombination of various method. For example, there may be extraction withan organic solvent, e.g. ether, ethyl acetate or chloroform; dissolutioninto a more polar solvent, e.g. acetone or alcohol; removal ofimpurities with a less polar solvent, e.g. petroleum ether or hexane,adsorptive chromatography with active carbon or silica gel; gelfiltration through a column of "sephadex" (available from Pharmacia Co.,Ltd, U.S.A.); and so on.

The instant compounds of this invention are unexpectedly potentantiparasitic agents against endo and ecto parasites, particularlyhelminths and arthropods, which cause numerous parasitic diseases inhumans, animals, and plants.

Parasitic diseases may be caused by either endoparasites orectoparasites. Endoparasites are those parasites which live inside thebody of the host, either within an organ (such as the stomach, lungs,heart, intestines, etc.) or simply under the skin. Ectoparasites arethose parasites which live on the outer surface of the host but stilldraw nutrients from the host.

The endoparasitic diseases generally referred to as helminthiasis aredue to infection of the host with parasitic worms known as helminths.Helminthiasis is a prevalent and serious worldwide economic problem dueto infection of domesticated animals such as swine, sheep, horses,cattle, goats, dogs, cats, and poultry. Many of these infections arecaused by the group of worms described as nematodes which cause diseasesin various species of animals throughout the world. These diseases arefrequently serious and can result in the death of the infected animal.The most common genera of nematodes infecting the animals referred toabove are Haemonchus, Trichostrongylus, Ostertagia, Nematodirus,Cooperia, Ascaris, Bunostomum, Oesophagostomum, Chabertia, Trichuris,Strongylus, Trichonema, Dictyocaulus, Capillaria, Heterakis, Toxocara,Ascaridia, Oxyuris, Ancylostoma, Uncinaria, Toxascaris, and Parascaris.Many parasites are species specific (infect only one host) and most alsohave a preferred site of infection within the animal. Thus Haemonchusand Ostertagia primarily infect the stomach while Nematodirus andCooperia mostly attack the intestines. Other parasites prefer to residein the heart, eyes, lungs, blood vessels, and the like while stillothers are subcutaneous parasites. Helminthiasis can lead to weakness,weight loss, anemia, intestinal damage, malnutrition, and damage toother organs. If left untreated these diseases can result in the deathof the animal.

Infections by ectoparasitic arthropods such as ticks, mites, lice,stable flies, hornflies, blowflies, fleas, and the like are also aserious problem. Infection by these parasites results in loss of blood,skin lesions, and can interfere with normal eating habits thus causingweight loss. These infections can also result in transmission of seriousdiseases such as encephalitis, anaplasmosis, swine pox, and the likewhich can be fatal.

Animals may be infected by several species of parasite at the same timesince infection by one parasite may weaken the animal and make it moresusceptible to infection by a second species of parasite. Thus acompound with a broad spectrum of activity is particularly advantageousin the treatment of these diseases. The compounds of this invention haveunexpectedly high activity against these parasites, and in addition, arealso active against Dirofilaria in dogs, Nematospiroides and Syphacia inrodents, biting insects and migrating dipterous larvae such as Hypodermasp. in cattle, and Gastrophilus in horses.

The instant compounds are also useful against endo and ecto parasiteswhich cause parasitic diseases in humans. Examples of such endoparasiteswhich infect man include gastro intestinal parasites of the generaAncylostoma, Necator, Ascaris, Strongyloides, Trichinella, Capillaria,Trichuris, Enterobius, and the like. Other endoparasites which infectman are found in the blood or in other organs. Examples of suchparasites are the filarial worms Wucheria, Brugia, Onchocerca, and thelike as well as extra intestinal stages of the intestinal wormsStrongylides and Trichinella. Ectoparasites which parasitize man includearthropods such as ticks, fleas, mites, lice, and the like and, as withdomestic animals, infections by these parasites can result intransmission of serious and even fatal diseases. The instant compoundsare active against these endo and ecto parasites and in addition arealso active against biting insects and other dipterous pests which annoyhumans. The instant compounds when administered orally or parenterallyare administered at a dosage rate of from 0.05 to 20 mg/kg of animalbody weight.

The instant compounds are also useful against common household pestssuch as Blatella sp. (cockroach), Tineola sp. (clothes moth), Attagenussp. (carpet beetle), Musca domestica (housefly) and against Solenopsisinvicta (imported fire ant).

The compounds are furthermore useful against agricultural pests such asaphids (Acyrthiosiphon sp.), locusts, and boll weevils as well asagainst insect pests which attack stored grains such as Tribolium sp.and against immature stages of insects living on plant tissue. Thecompounds are also useful as a nematocide for the control of soilnematodes which may be agriculturally important.

For use as an antiparasitic agent in animals the instant compounds maybe administered internally either orally or by injection, or topicallyas a liquid drench or as a shampoo.

For oral administration, the compounds may be administered in capsule,tablet, or drench bolus form or alternatively they can be mixed in theanimals feed. The capsules, tablets, and drenches boluses are comprisedof the active ingredient in combination with an appropriate carriervehicle such as starch, talc, magnesium stearate, or di-calciumphosphate. These unit dosage forms are prepared by intimately mixing theactive ingredient with suitable finely-powdered inert ingredientsincluding diluents, fillers, disintegrating agents, suspending agents,and/or binders such that a uniform mixture solution or suspension isobtained. An inert ingredient is one that will not react with theinstant compounds and which is non toxic to the animal being treated.Suitable inert ingredients include starch, lactose, talc, magnesiumstearate, vegetable gums and oils, and the like. These formulations maycontain a widely variable amount of the active and inactive ingredientsdepending on numerous factors such as the size and type of the animalspecies to be treated and the type and severity of the infection. Theactive ingredient may also be administered as an additive to the feed bysimply mixing the compound with the feedstuff or by applying thecompound to the surface of the feed. Alternatively the active ingredientmay be mixed with an inert carrier and the resulting composition maythen either be mixed with the feed or fed directly to the animal.Suitable inert carriers include corn meal, citrus meal, fermentationresidues, soya grits, dried grains and the like. The active ingredientsare intimately mixed with these inert carriers by grinding, stirring,milling, or tumbling such that the final composition contains from 0.001to 5.0% by weight of the active ingredient.

The compounds may alternatively be administered parenterally viainjection of a formulation consisting of the active ingredient dissolvedin an inert liquid carrier. Injection may be either intramuscular,intraruminal, intratracheal, or subcutaneous. The injectable formulationconsists of the active ingredient mixed with an appropriate inert liquidcarrier. Acceptable liquid carriers include the vegetable oils such aspeanut oil, cotton seed oil, sesame oil and the like as well as organicsolvents such as solketal, glycerol formal and the like. As analternative, aqueous parenteral formulations may also be used. Thevegetable oils are the preferred liquid carriers. The formulations areprepared by dissolving or suspending the active ingredient in the liquidcarrier such that the final formulation contains from 0.005 to 20% byweight of the active ingredient.

Topical application of the instant compounds is possible through the useof a liquid drench or a shampoo containing the instant compounds as anaqueous solution or suspension. These formulations generally contain asuspending agent such as bentonite and normally will also contain anantifoaming agent. Formulations containing from 0.005 to 20% by weightof the active ingredient are acceptable. Preferred formulations arethose containing from 0.5 to 5% by weight of the instant compounds.

The instant compounds are primarily useful as antiparasitic agents forthe treatment and/or prevention of helminthiasis in domestic animalssuch as cattle, sheep, horses, dogs, cats, goats, swine, and poultry.They are also useful in the prevention and treatment of parasiticinfections of these animals by ectoparasites such as ticks, mites, lice,fleas and the like. They are also effective in the treatment ofparasitic infections of humans. In treating such infections thecompounds of this invention may be used individually or in combinationwith each other or with other unrelated antiparasitic agents. The dosageof the instant compounds required for best results depends on severalfactors such as the species and size of the animal, the type andseverity of the infection, the method of administration and the compoundused. Oral administration of the instant compounds at a dose level offrom 0.005 to 50 mg per kg of animal body weight either in a single doseor in several doses spaced a few days apart, generally gives goodresults. A single dose of one of the instant compounds normally givesexcellent control however repeat doses may be given to combatre-infection or for parasite species which are unusually persistent. Thetechniques for administering these compounds to animals are known tothose skilled in the veterinary field.

The compounds of this invention may also be used to combat agriculturalpests which attack crops either in the field or in storage. Thecompounds are applied for such uses as sprays, dusts, emulsions and thelike either to the growing plants or the harvested crops. The techniquesfor applying these compounds in this manner are known to those skilledin the agricultural arts.

The following examples are provided in order that this invention mightbe more fully understood; they are not to be construed as limitative ofthe invention.

Procedure No. 1: Production and Isolation of Marcfortine A

Seed Fermentation Process

Seed fermentations are inoculated using agar plugs of isolatePenicillium sp. UC 7780 (NRRL 18887) stored over liquid nitrogen. Threeplugs are thawed and used as inoculum. GS-7 is composed of glucose andcottonseed flour (sold under the trademark "Pharmamedia" by TradersProtein, Procter & Gamble Oilseed Products Co., Memphis, Tenn., U.S.A.).Unsupplemented tap water is used to hydrate the medium components andthe medium is adjusted to pH 7.2 with NH₄ OH. The medium is dispensedinto unbaffled closed-system flasks at 300 ml pper 1000 ml flask, andsterilized by autoclaving at 121° C. for 30 minutes. Each closed-systemflask containing 300 ml of GS-7 medium is inoculated with three agarplugs of Penicillium sp. UC 7780 (NRRL 18887) and shaken on a rotaryshaker at 250 rpm for 36 hr at 22° C.

Secondary Seed Fermentation Process

The mature seed cultures are used as inoculum for the secondary mediumat a 0.3% seed rate. The secondary medium is composed of glucosemonohydrate (sold as under the trademark Cerelose by C.P.C.International) 25 g, cottonseed flour (sold under the trademark"Pharmamedia") 25 g, MgCl₂.6H₂ O 329.8 mg, MnSO₄.H₂ O 11.4 mg, FeSO₄.7H₂O 3.2 mg, Na₂ MoO₄.2H₂ O 1.8 mg, CaCl₂.2H₂ O 367.6 mg, NaCl 84.2 mg, KCl5.8 mg, ZnSO₄.7H₂ O 0.1 mg, CoCl₂.6H₂ O 0.1 mg, CuSO₄.5H₂ O 3.1 mg, andsilicone antifoam (sold under the trademark SAG-471 Antifoam) 0.5 ml perliter of reverse-osmosis grade water. Medium components sufficient for200 liters of secondary seed medium are hydrated in reverse-osmosisgrade water to a q.s. volume of 190 liters in a 250-L fermentor. Afterformulation, the pH of the medium is adjusted to pH 7.2 with NH₄ OH, andthen the medium is sterilized at 121° C. for 30 minutes. Twoclosed-system flasks of the mature primary-seed culture are used asinoculum at a 0.3% seed rate. The secondary seed culture is incubated atat 22° C., with 125 slm aeration, 5 psig backpressure, and 250 rpm for36 hours.

Production Fermentation Process

The production medium is composed of beet molasses 50 g, fish meal (soldunder the trademark Menhaden Select Fish Meal) 16 g, yeast extract (soldunder the trademark Fidco) 10 g, MgCl₂.6H₂ O 329.8 mg, MnSO₄.H₂ O 11.4mg, FeSO₄.7H₂ O 3.29 mg, Na₂ MoO₄.2H₂ O 1.8 mg, CaCl₂.2H₂ O 367.6 mg,NaCl 84.2 mg, KCl 5.8 mg, ZnSO₄.7H₂ O 0.1 mg, CoCl₂.6H₂ O 0.1 mg,CuSO₄.5H₂ O 3.1 mg, and silicone antifoam (sold under the trademarkSAG-471 Antifoam) 0.5 ml per liter of reverse-osmosis grade water.

Medium components sufficient for 5,000 liters of medium are hydrated inreverse-osmosis grade water to a q.s. volume of 4,700 liters in a 5,000L fermentor. After formulation, the pH of the medium is adjusted to pH7.0 with KOH, and then the medium is sterilized at 123° C. for 30minutes. The mature secondary-seed culture is used as inoculum at a 1.0%seed rate. The culture is incubated at 22° C., with 2,500 slm aeration,5 psig backpressure, and 250 rpm for 96 hours.

Isolation of Marcfortine A:

The 4900 L fermentation volume is harvested by passing through a highshear mixer to the harvest vessel. Following transfer, 4% wt./v. ofdiatomaceous earth and 1/2 volume of methylene chloride are added. Theharvest solution is then filtered using a filter press. The filter cakeis washed 2 times with a 10% volume of methylene chloride.

The filtrate obtained is decanted to remove the water (aqueous) phase.The remaining product-rich methylene chloride phase is then concentratedto a volume of 44 L. The concentrate is then polished using a 20%concentrate volume (9 L)of methylene chloride and diatomaceous earthover a filter.

The 53 L polished concentrate is further purified to separateMarcfortine A from other components by silica gel chromatography andcrystallization.

Before chromatography, the polished concentrate is divided into fourapproximately equal aliquots. Each aliquot is chromatographed over anewly packed 9" diameter column prepared from 25 Kg of dry silica gel(bed volume 59 L). The loaded columns are eluted with 120 L of 10%acetone in methylene chloride, 120 L of 20% acetone in methylenechloride, 120 L of 30% acetone in methylene chloride, 160 L of 40%acetone in methylene chloride, and 130 L of acetone collecting the 30and 40% eluates as 20 L fractions. Eluates are monitored by TLC, usingfor example a solvent system comprised of 6% isopropanol and 0.3%ammoniumn hydroxide in methylene chloride to develop Whatman LK6DFsilica gel plates. Fractions of Marcfortine A (containing a small amountof Marcfortine D which co-chromatographs with D) are crystallized fromacetone. Appropriate fractions (40-100 L) are concentrated under reducedpressure to a volume of approximately 5 L. The solution (or lightslurry) is then transferred to a rotatory evaporater and concentrationcontinued under reduced pressure. Several 1 L portions of acetone areadded during the course of the concentration until the methylenechloride is completely displaced. The resulting acetone slurry(approximately 1 L volume) is refrigerated overnight, and the crystalsof Marcfortine A are collected and washed with several small portions ofcold acetone, and dried under vacuum. Such crystals may be contaminatedwith several percent of Marcfortine D. Repeated recrystallization frommethylene chloride/acetone (displacing methylene chloride as described)affords pure Marcfortine A.

Isolation of marcfortine D

The 4900 L fermentation volume is harvested by passing through a highshear mixer to the harvest vessel. Following transfer, 4% wt./v. ofdiatomaceous earth and 1/2 volume of methylene chloride are added. Theharvest solution is then filtered using a filter press. The filter cakeis washed 2 times with a 10% volume of methylene chloride.

The filtrate obtained is decanted to remove the water (aqueous) phase.The remaining product-rich methylene chloride phase is then concentratedto a volume of 44 L. The concentrate is then polished using a 20%concentrate volume (9 L)of methylene chloride and diatomaceous earthover a filter.

The 53 L polished concentrate is further purified to separateMarcfortine A from other components by silica gel chromatography andcrystallization.

Before chromatography, the polished concentrate is divided into fourapproximately equal aliquots. Each aliquot is chromatographed over anewly packed 9" diameter column prepared from 25 Kg of dry silica gel(bed volume 59 L). The loaded columns are eluted with 120 L of 10%acetone in methylene chloride, 120 L of 20% acetone in methylenechloride, 120 L of 30% acetone in methylene chloride, 160 L of 40%acetone in methylene chloride, and 130 L of acetone collecting the 30and 40% eluates as 20 L fractions. Eluates are monitored by TLC, usingfor example a solvent system comprised of 6% isopropanol and 0.3%ammoniumn hydroxide in methylene chloride to develop Whatman LK6DFsilica gel plates. Fractions of marcfortine A containing marcfortine Dare concentrated. One gram of this material is dissolved in formic acid(20 mL, 93%) and standing at room temperature for 16 h. After thevolatile components are removed with reduced pressure, the residue issubjected to silica gel chromatography (1:20 MeOH:CH₂ Cl₂) to givemarcfortine D (100 mg) as a white solid. The structure of the productcan be confirmed by NMR spectroscopy and mass spectrometry. HRMS (FAB)M/Z M+H! calculated for C₂₈ H₃₅ N₃ O₃ +H: 462.2756; measured: 462.2739.

Procedure 1A Production and Isolation of Marcfortines A and C

Primary Seed Fermentation Process

Seed fermentations are inoculated using agar plugs of isolatePenicillium sp. UC 7780 (NRRL 18887) stored over liquid nitrogen. Threeplugs are thawed and used as inoculum for 100 ml of GS-7 seed medium.GS-7 is composed of glucose and cottonseed flour (sold under thetrademark "Pharmamedia" by Traders Protein, Procter & Gamble OilseedProducts Co., Memphis, Tenn., U.S.A.) each added at a concentration of25 g/L of tap water. After formulation, the pH of GS-7 is adjusted to7.2 using NH₄ OH. The medium is autoclaved in 100 ml volumes in 500 mlunbaffled fermentation flasks for 30 min. Sterile GS-7 is inoculated asdescribed above and shaken at 250 rpm for 35-58 hr at 23° C.

Production Fermentation Process (shaker flask)

The mature seed cultures are used as inoculum for the production mediumat a 1% seed rate. The production medium is composed of glucose 45 g,enzymatically digested casein (sold under the trademark Peptonized MilkNutrient by Sheffield Products, Norwich, N.Y., U.S.A.) 25 g, yeastextract (sold under the trademark BACTO Yeast Extract Code: 0127 byDifco Laboratories, Detroit, Mich.) 2.5 g per liter of tap water. Afterformulation, the pH of the production medium is adjusted to 7.0 usingpotassium hydroxide. This medium is then autoclaved for 30 min in 100 mlvolumes contained in 500 ml baffled fermentation flasks. Sterileproduction medium is inoculated as described above, and shaken for 7-14days at 250 rpm at 21° C.

Production Fermentation Process (Labraferm tanks)

The mature seed cultures are used as inoculum for the sterile productionmedium at a 0.5% seed rate. The production medium is described above.After pH adjustment to 7.0 using KOH, 10 L of this medium are autoclavedfor 90 min in 12 L Labraferm tanks (New Brunswick Scientific Co., Inc.).The tanks are inoculated at a 0.5% seed rate and stirred at 500 rpm at20° C. for 5-9 days. The air flow rate is maintained between 10-15L/min.

Isolation of Marcfortines A and C

Whole fermentation broth (35 1) is macerated at low speed in a largecommercial Waring Blender and then blended with an equal volume ofmethylene chloride. The mixture is stored overnight under refrigerationand then subjected to centrifugation to break the emulsion. Theresulting clear methylene chloride layer is drawn off and evaporatedunder reduced pressure. A concentrated solution of the residue (37.4 g)in methylene chloride is applied to a column of silica gel (1 Kg) slurrypacked in methylene chloride. The column is eluted with increasingconcentrations of acetone in methylene chloride (10%, 20%, 30%, 40%, and50% acetone). Fractions are monitored by TLC and appropriate fractionsevaporated and crystallized from acetone to give Marcfortine A andMarcfortine C.

Procedure 1B Production and Isolation of Marcfortines A and C

Seed Fermentation Process

Seed fermentations are inoculated using agar plugs of isolatePenicillium sp. UC 7780 (NRRL 18887) stored over liquid nitrogen. Threeplugs are thawed and used as inoculum for 100 ml of GS-7 seed medium.GS-7 is composed of glucose and cottonseed flour (sold under thetrademark "Pharmamedia" by Traders Protein, Procter & Gamble OilseedProducts Co., Memphis, Tenn., U.S.A.) each added at a concentration of25 g/L of tap water. After formulation, the pH of GS-7 is adjusted to7.2 using NH₄ OH. The medium is autoclaved in 100 ml volumes in 500 mlunbaffled fermentation flasks for 30 min. Sterile GS-7 is inoculated asdescribed above and shaken at 250 rpm for 35-58 hr at 23° C.

Production Fermentation Process (Shake Flask)

The mature seed cultures are used as inoculum for the production mediumat a 1% seed rate. The production medium is composed of glucose 20 g,glycerol 15 ml, cottonseed flour (sold under the trademark "Pharmamedia"by Traders Protein, Procter & Gamble Oilseed Products Co., Memphis,Tenn., U.S.A.) 20 g, soybean meal 10 g, and K₂ HPO₄ 3 g per liter of tapwater. After formulation, the pH of the production medium is adjusted to6.8 using potassium hydroxide. This medium is then autoclaved for 30 minin 100 ml volumes contained in 500 ml baffled fermentation flasks.Sterile production medium is inoculated as described above, and shakenfor 7-14 days at 250 rpm at 21° C.

Production Fermentation Process (Labraferm tanks)

The mature seed cultures are used as inoculum for the sterile productionmedium at a 0.5% seed rate. The production medium is described above.After pH adjustment to 7.0 using KOH, 10 L of this medium are autoclavedfor 90 min in 12 L Labraferm tanks (New Brunswick Scientific Co., Inc.).The tanks are inoculated at a 0.5% seed rate and stirred at 500 rpm at20° C. for 5-9 days. The air flow rate is maintained between 10-15L/min.

Isolation of Marcfortines A and C

Whole fermentation broth (35 l) is macerated at low speed in a largecommercial Waring Blender and then blended with an equal volume ofmethylene chloride. The mixture is stored overnight under refrigerationand then subjected to centrifugation to break the emulsion. Theresulting clear methylene chloride layer is drawn off and evaporatedunder reduced pressure. A concentrated solution of the residue (37.4 g)in methylene chloride is applied to a column of silica gel (1 Kg) slurrypacked in methylene chloride. The column is eluted with increasingconcentrations of acetone in methylene chloride (10%, 20%, 30%, 40%, and50% acetone). Fractions are monitored by TLC and appropriate fractionsevaporated and crystallized from acetone to give Marcfortine A andMarcfortine C.

Synthesis of 14-substituted marcfortines

Treatment of marcfortine A (Formula 1a, Chart A) with cyanogen iodideproduces a mixture (Formula 5) of 16α-iodo-17β-cyanomarcfortine A and160-iodo-17α-cyanomarcfortine A which can be separated by silica gelchromatography. Dehydroiodination of this mixture with potassiumhydroxide in methanol leads to 16,17-dehydro-17-cyanomarcfortine A(Formula 6) which is oxidized by selenium dioxide to 17-ketomarcfortineA (Formula 7). Introduction of a double bond between C15 and C16 isaccomplished by selenation of position-16 (phenyl selenyl chloride andLDA) followed by oxidation of the selenium intermediate with hydrogenperoxide. Subsequent elimination of the phenylselenic acid gives15,16-dehydro-17-ketomarcfortine A (Formula 8). This compound is a keyintermediate in the synthesis of 14α-hydroxymarcfortine A (Formula 10)to which it can be converted by either of two distinct synthetic routes.

In the first route allylic oxidation of position-14 of this materialusing potassium bis(trimethylsilyl)amide and2-phenylsulfonyl-3-phenyloxaziridine is accompanied by oxidation ofposition-16 to give a mixture of the required14α-hydroxy-15,16-dehydro-17-ketomarcfortine A (Formula 9a) and14,15-dehydro-16-hydroxy-17-ketomarcfortine A (Formula 9b). These twoproducts are separated by silica gel chromatography. The compound ofFormula 9a is reduced by means of lithium aluminum hydride in THF to14α-hydroxymarcfortine A (Formula 10), a title compound of thisinvention disclosure. Alternatively, the compound of Formula 8 (Chart B)is oxidized with selenium dioxide in dioxane to afford a 2:1 mixture of14α-hydroxy-15,16-dehydro-17-ketomarcfortine A (Formula 9a) and15,16-dehydro-14,17-diketomarcfortine A (Formula 11). These areseparated by means of silica gel chromatography. Each of these compoundsis independently converted to 14α-hydroxy-17-ketomarcfortine A (Formula12a): the compound of Formula 9a by reduction of the 15,16-double bondwith lithium triethylborohydride; the compound of Formula 11 byreduction of the carbonyl at position 14 with lithium borohydride. Inthe latter case, an equal amount of 14β-hydroxy-17-ketomarcfortine A(Formula 12b) is also produced which is removable by chromatography. Thecompound of formula 12a is reduced with borane tetrahydrofuran (THF)complex to give 14α-hydroxymarcfortine A (Formula 10).

14α-Hydroxy-15,16-dehydro-17-ketomarcfortine A (Formula 9a, Chart C) isreduced with lithium triethylborohydride to14α-hydroxy-17-ketomarcfortine A (Formula 12a). This is transformed bymeans of a Swern oxidation using oxalyl chloride and DMSO to14,17-diketomarcfortine A (Formula 13). Treatment with methylmagnesiumbromide in a Grignard reaction produces a mixture of14α-hydroxy-14β-methyl-17-ketomarcfortine A (Formula 14a) and14β-hydroxy-14α-methyl-17-ketomarcfortine A (Formula 14b) which areseparated by silica gel chromatography. The ratio of the products isdependent upon the solvent used: methylene chloride gives a 6:1 ratio,while THF gives a >50:1 ratio, respectively. Reduction of the compoundof Formula 13a with lithium aluminum hydride gives14α-hydroxy-14β-methylmarcfortine A (Formula 15).

Swern oxidation of 14α-hydroxymarcfortine A (Formula 10, Chart D)provides 14-ketomarcfortine A (Formula 16), which is reduced with sodiumborohydride to 14-β-hydroxymarcfortine A (Formula 17). Treatment of14-ketomarcfortine A (Formula 16) with ethylmagnesium bromide in agrignard reaction produces 14α-hydroxy-14-ethylmarcfortine A (Formula19). Treatment of 14α-hydroxymarcfortine A (Formula 10) withm-chloroperoxybenzoic acid produces 14α-hydroxymarcfortine A N-oxide(Formula 18). 14β-methylmarcfortine A can be prepared from14α-hydroxy-14β-methylmarcfortine A by means of dehydroxylation. Thus,14α-hydroxy-14β-methylmarcfortine A is treated withphenylchlorothionoformate in the presence of base. This thionoformatederivative of 14α-hydroxy-14β-methylmarcfortine A is reduced withtri-n-butyltin hydride to produce 14β-methylmarcfortine A.

Alternatvely, 14α-hydroxymarcfortine A can be synthesized frommarcfortine A (Chart E). Treatment of marcfortine A with sodiumbicarbonate and iodine in aqueous tetrahydrofuran produces17-ketomarcfortine A (Formula 7), which can be disulfenylated by usingLDA and phenyl disulfide to give 16-dithiophenyl-17-keto marcfortine A(Formula 20, chart E) in 60% yield from marcfortine A. Oxidation withm-chloroperoxybenzoic acid produces16-thiophenyl-16-sulfoxyphenyl-17-ketomarcfortine A (Formula 21), whicheliminates in refluxing toluene to yield15,16-dehyro-16-thiophenyl-17-ketomarcfortine A (Formula 22). Subsequenttreatment with m-chloroperoxybenzoic acid produces15,16-dehydro-16-sufoxyphenyl-17-ketomarcfortine A (Formula 23), whichundergoes rearrangement by using diethyl amine in methanol to produce15,16-dehydo-14α-hydroxy- 17-ketomarcfortine A (Formula 9a).

14α-Hydroxy-15α-methylmarcfortine A (Formula 35, Chart G) can besynthesized from 15,16-dehydro-14α-hydroxy-17-ketomarcfortine A (Formula9a, Chart G). Thus, 15,16-dehydro-14α-hydroxy-17-ketomarcfortine A(Formula 9a) is treated with either methylmagnesium bromide or lithiumdimethylcopper to produce 15α-methyl-14α-hydroxy-17-ketomarcfortine A(Formula 34), which is reduced with borane-dimethylsulfide complex toproduce 15α-methyl-14α-hydroxymarcfortine A (Formula 35).15α-Methyl-14α-hydroxy-17-ketomarcfortine A (Formula 34) is transformedby means of a Swern Oxidation using oxalyl chloride and DMSO to15α-methyl-14,17-diketomarcfortine A (Formula 36). Treatment withmethylmagnesium bromide in a Grignard reaction produces15α-Methyl-14α-hydroxy-14β-methyl-17-ketomarcfortine A (Formula 37),which is reduced with borane-dimethylsulfide complex to produce15α-methyl-14α-hydroxy-14β-methylmarcfortine A (Formula 38).

These previoulsy described procedures can be used to produce14-substituted marcfortine B, C and D derivatives.

Preparation of 16-iodo-17-cyanomarcfortine A as a mixture ofdiastereomers (Formula 5)

Solid cyanogen iodide (11.7 g, 76.5 mmol) is added to a solution ofmarcfortine A (10.5 g, 22 mmol) in CHCl₃ (150 mL) and the reactionmixture heated under reflux until all of the marcfortine A has beenconsumed (about 5 h). The resulting black solution is cooled to roomtemperature, diluted with CH₂ Cl₂ (100 mL), washed with sat NaHCO₃, andthen washed with a solution of Na₂ SO₃. The organic phase is separated,dried over MgSO₄, and concentrated to dryness. The resulting crude solidis subjected to silica gel chromatography (3:2-EtOAc: hexane) to give16-Iodo-17-cyanomarcfortine A (12.5 g, 90%) as a white powdery solid.The structure of the product can be confirmed by nuclear magneticresonance spectroscopy and mass spectrometry.

Preparation of 16,17-dehydro-17-cyanomarcfortine A (Formula 6)

16-Iodo-17-cyanomarcfortine A (9.5 g, 15 mmol) is dissolved in MeOH (150mL), and aqueous KOH (45%, 3 mL) is added. The reaction mixture isstirred at room temperature for 2 h. Water is added and the resultingwhite precipitate collected by filtration, washed with water, and driedovernight under vacuum to give 16,17-Dehydro-17-cyanomarcfortine A (6.6g, 75%) as a white powder. The structure of the product can be confirmedby nuclear magnetic resonance spectroscopy and mass spectrometry. MS(FAB) M/Z M+H!: 501.

Preparation of 17-ketomarcfortine A (Formula 7)

Selenium dioxide (2.9 g, 26 mmol) is added to a solution of16,17-Dehydro-17-cyanomarcfortine A (6.0 g, 10 mmol) in 95% EtOH (100mL) and the reaction mixture stirred at room temperature for 2 h. Thereaction is quenched by adding sat NaHCO₃ (100 mL). The resultingmixture is extracted with CH₂ Cl₂ (2×200 mL). The extracts are combined,dried (MgSO₄), and concentrated to give 7 g of crude product. Thismaterial is purified by silica gel chromatography (EtOAc) to give17-ketomarcfortine A (3.6 g, 75%) as a white solid. The structure of theproduct can be confirmed by nuclear magnetic resonance spectroscopy andmass spectrometry. HRMS (FAB) M/Z M+H! calculated for C₂₈ H₃₃ N₃ O₅ +H:492.2498; measured: 492.2478.

Alternatively, and more preferably, the title compound can besynthesized by using p-toluenesufonic acid. Thus, p-toluenesulfonic acidmonohydrate (1 g) is to a solution of 16,17-dehydro-17-cyanomarcfortineA (10 g) in 95% MeOH (50 mL) and the reaction mixture stirred at roomtemperature for 1 h. Triethyl amine (2 mL) is added to the mixture andthe solvent was evaporated. The residue is triturated with 10% aqueoussodium carbonate solution (100 mL) and the solid is filter and dried togive the tiltle compound as a solid (90% yield). The structure of theproduct can be confirmed by nuclear magnetic resonance spectroscopy andmass spectrometry.

Preparation of 15,16-dehydro-17-ketomarcfortine A (Formula 8)

A solution of lithium diisopropylamide is prepared from a solution ofn-butyl lithium (1.6 M, 9.9 mL, 15.4 mmol) in hexane anddiisopropylamine (2.2 mL, 15.7 mmol). This is diluted with anhydroustetrahydrofuran (THF, 20 mL) and cooled to at -78° . A solution of17-ketomarcfortine A (2.0 g, 4.1 mmol) in anhydrous THF (20 mL) is addeddropwise and the reaction mixture allowed to warm to -40° during 1 h.The mixture is again cooled to -78° and treated dropwise with phenylselenium chloride (19 mg, 5.2 mmol) in THF (10 mL). After 5 min thereaction is quenched with sat NaHCO₃, extracted with CH₂ Cl₂, dried(MgSO₄), and concentrated to give a yellow solid which can be usedwithout further purification. This material is dissolved in THF (150 mL)and treated with H₂ O₂ (30%, 1.5 mL) at 0°. The cooling bath is removedand the reaction mixture stirred for 30 min at room temperature. Thereaction is quenched by adding NaOH (1N, 100 mL). The mixture isextracted with CH₂ Cl₂ (2×200 mL). The extracts are combined, dried(MgSO₄), and concentrated to give crude product. This material ispurified by silica gel chromatography (EtOAc) to give15,16-dehydro-17-ketomarcfortine A (1.3 g,65%) as a white solid. Thestructure of the product is confirmed by nuclear magnetic resonancespectroscopy and mass spectrometry. HRMS (FAB) M/Z M+H! calculated forC₂₈ H₃₁ N₃ O₅ +H: 490.2342; measured: 490.2345.

Preparation of 14α-hydroxy-15,16-dehydro-17-ketomarcfortine A (Formula9a) using oxaziridine chemistry

A solution of potassium bis(trimethylsilyl)amide in toluene (0.5M, 1 mL,0.5 mmol) is added dropwise to a solution of15,16-dehydro-17-ketomarcfortine A (66 mg, 0.14 mmol) in THF (2 mL) at-78°. The resulting pale yellow, turbid solution is allowed to warm to-40° during 1 h. The reaction mixture is cooled -78°, stirred 15 min,and then treated by the dropwise addition of a solution of2-phenylsulfonyl-3-phenyloxaziridine (42 mg, 0.16 mmol) in THF (2 mL).The mixture is stirred 5 min after which the reaction is quenched byadding NaHCO₃. The mixture is extracted with CH₂ Cl₂ (2×25 mL). Theextracts are combined, dried (MgSO₄), and concentrated to give crudematerial. This is purified by preparative thin layer chromatography(silica gel, EtOAc) to give 14α-Hydroxy-15,16-dehydro-17-ketomarcfortineA (8 mg, 12%) as a white solid. The structure can be confirmed bynuclear magnetic resonance spectroscopy and mass spectrometry. HRMS(FAB) M/Z M+H! calculated for C₂₈ H₃₁ N₃ O₆ +H: 506.2291; measured:506.2280. 14,15-Dehydro-16-hydroxy-17-ketomarcfortine A (14 mg, 20%) isalso obtained from the layer. Its structure can be confirmed by nuclearmagnetic resonance spectroscopy.

Preparation of 14α-hydroxy-15,16-dehydro-17-ketomarcfortine A (Formula9a), 15,16-dehydro-14,17-diketomarcfortine A (Formula 11) and14,15-dehydro- 16,17-diketomarcfortine A (Formula 24) using seleniumdioxide

15,16-Dehydro-17-ketomarcfortine A (1.29 g, 2.6 mmol) is dissolved inp-dioxane (30 mL) and treated with selenium dioxide (390 mg). Themixture is refluxed for 1 h and the solvent evaporated in vacuo. Theresidue is triturated with methylene chloride (30 mL) and filtered. Thefiltrate is concentrated, and the residue subjected to silica gelchromatography (1:20 MeOH:EtOAc) to give14α-hydroxy-15,16-dehydro-17-ketomarcfortine A (430 mg, 32%) as a solid.15,16-Dehydro-14,17-diketomarcfortine A (Formula 11, 212 mg, 16%) isalso obtained from the chromatography.14,15-Dehydro-16,17-diketomarcfortine A (Formula 24, 106 mg, 8%) is alsoobtained from the chromatography. The structure of these products can beconfirmed by nuclear magnetic resonance spectroscopy and massspectrometry.

Conversion of 14α-hydroxy-15,16-dehydro-17-ketomarcfortine A (Formula9a) to 15,16-dehydro-14,17-diketomarcfortine A (Formula 11)

14α-Hydroxy-15,16-dehydro-17-ketomarcfortine A (60 mg, Formula 9a) isdissolved in methylene chloride (10 mL) and treated with manganesedioxide (60 mg). The mixture is stirred at room temperature for 1 h andconcentrated. Preparative thin layer chromatography of the residue onsilica gel (50% methylene chloride in EtOAc) afforded15,16-dehydro-14,17-diketomarcfortine A (Formula 11, 35 mg, 60%). Thestructure of these products can be confirmed by nuclear magneticresonance spectroscopy and mass spectrometry.

EXAMPLE 1

Preparation of 14ac-hydroxymarcfortine A (Formula 10)

14α-Hydroxy-15,16-dehydro-17-ketomarcfortine A (20 mg, 0.040 mmol) isdissolved in THF (5 mL) and treated with a solution of Lithium AluminumHydride (1M, 0.11 mL, 0.11 mmol) in THF at 0°. The mixture is stirredfor 0.5 h at 0° after which a solution of NaHCO₃ (10%) is added. Themixture is extracted with CH₂ Cl₂ (2×10 mL). The extracts are combined,dried (MgSO₄), and the solvent evaporated. Preparative thin layerchromatography of the residue on silica gel (10% MeOH in EtOAc) afforded14α-hydroxymarcfortine A (3 mg, 15%) as a white solid. The structure ofthe product can be confirmed by nuclear magnetic resonance spectroscopyand mass spectrometry. HRMS (FAB) M/Z M+H! calculated for C₂₈ H₃₅ N₃ O₅+H: 494.2655; measured: 494.2653.

Preparation of 14α-hydroxy-17-ketomarcfortine A (Formula 12a) from14α-hydroxy-15,16-dehydro-17-ketomarcfortine A (Formula 9a)

14α-Hydroxy-15,16-dehydro-17-ketomarcfortine A (50 mg, 0.1 mmol) isdissolved in THF (5 mL) and treated with a solution of lithiumtriethylborohydride in THF (1M, 0.7 mL) at -78°. The mixture is stirredfor 0.5 h at -78°. The reaction is quenched by adding MeOH (1 mL), andthe mixture is concentrated. The resulting solid is subjected to silicagel chromatography (1:20 MeOH:CH₂ Cl₂) to give 14α-hydroxy-17-ketomarcfortine A (43 mg, 86%) as a white solid. The structure of theproduct can be confirmed by NMR spectroscopy and mass spectrometry. HRMS(FAB) M/Z M+H! calculated for C₂₈ H₃₃ N₃ O₆ +H: 508.2447; measured:508.2437.

Preparation of 14α-hydroxy-17-ketomarcfortine A (Formula 12a) from15,16-dehydro-14,17-diketomarcfortine A (Formula 11)

15,16-Dehydro-14,17-diketomarcfortine A (470 mg, 0.93 mmol) is dissolvedin THF and treated with a solution of lithium borohydride in THF (1M, 2mL) at room temperature. The mixture is stirred for 2 h after which asolution of NaHCO₃ (10%) is added. The mixture is extracted with CH₂ Cl₂(2×20 mL). The extracts are combined, dried (MgSO₄), and the solventevaporated. The residue contains a mixture of the two epimers which arereadily separated by silica gel chromatography (1:20 MeOH: EtOAc):14α-hydroxy-17-ketomarcfortine A (90 mg, 19%) and14β-hydroxy-17-ketomarcfortine A (94 mg, 20%). The structure of bothproducts can be confirmed by NMR spectroscopy and mass spectrometry.

Preparation of 14α-hydroxymarcfortine A (Formula 10) from14α-hydroxy-17-ketomarcfortine A (Formula 12a)

14α-Hydroxy-17-ketomarcfortine A (413 mg, 0.81 mmol) is dissolved in THF(20 mL) and treated with a solution of borane THF complex in THF (1M,2.43 mL) at 0°. The mixture is stirred for 2.25 h. The mixture isstirred for 0.5 h after which MeOH (3 mL) is added. After the solvent isevaporated, the residue is subjected to silica gel chromatography (1:16MeOH:EtOAc) to give 14α-hydroxymarcfortine A (250 mg, 92% yield based onstarting material recovered) and 14α-hydroxy-17-ketomarcfortine A(starting material, 140 mg, 34%).

Preparation of 14,17-diketomarcfortine A (Formula 13)

A solution of oxalyl chloride (40 μL) in anhydrous CH₂ Cl₂ (5 mL) istreated with dimethyl sulfoxide (45 μL) at -78°. The mixture is stirredfor 1 h at -78°. A solution of 14α-hydroxy-17-ketomarcfortine A (27 mg)in CH₂ Cl₂ (2 mL) is added dropwise. The reaction mixture is stirred 20min at -78°. Triethylamine (0.3 mL) is added to the reaction mixturewhich is allowed to warm to room temperature during 20 min. The mixtureis partitioned between 10% Na₂ CO₃ (10 mL) and CH₂ Cl₂ (10 mL). Theorganic layer is dried (MgSO4) and concentrated. The residue issubjected to silica gel chromatography (1:20 MeOH:CH₂ Cl₂) to give14,17-Diketomarcfortine A (22 mg, 80%) as a white solid. The structureof the product can be confirmed by NMR spectroscopy and massspectrometry. HRMS (FAB) M/Z M+H! calculated for C₂₈ H₃₁ N₃ O₆ +H:506.2291; measured: 506.2280.

Preparation of 14α-hydroxy-14β-methyl-17-ketomarcfortine A (Formula 14a)

A solution of 14,17-Diketomarcfortine A (16 mg, 0.032 mmol) in CH₂ Cl₂(5 mL) at -78° is treated with a solution of methylmagnesium bromide(3M, 0.16 mL, 0.48 mmol) in Et₂ O at -78°. The resulting mixture isstirred for 0.5 h at -78°. The reaction is quenched by adding 10% Na₂CO₃ (a few drops). The mixture was diluted with CH₂ Cl₂ (10 mL), dried(MgSO₄), and concentrated. The residue is subjected to silica gelchromatography (1:20 MeOH:CH₂ Cl₂) to give14α-hydroxy-14β-methyl-17-ketomarcfortine A (8 mg, 50%, R_(f) =0.25) asa white solid. The structure of the product can be confirmed by NMRspectroscopy and mass spectrometry. HRMS (FAB) M/Z M+H! calculated forC₂₉ H₃₅ N₃ O₆ +H: 522.2604; measured: 522.2620. Also obtained from thelayer is 14β-hydroxy-14α-methyl-17-ketomarcfortine A (1.2 mg, 7%, R_(f)=0.4) as a white solid. The structure of the product can be confirmed byNMR spectroscopy and mass spectrometry. HRMS (FAB) M/Z M+H! calculatedfor C₂₉ H₃₅ N₃ O₆ +H: 522.2604; measured: 522.2630. The 6:1 ratio ofproducts thus obtained is increased to greater than 50:1 and the yieldincreased to 80% when THF is used as the reaction solvent in place ofCH₂ Cl₂.

EXAMPLE 2

Preparation of 14α-hydroxy-14β-methylmarcfortine A (Formula 15)

A solution of 14α-hydroxy-14β-methyl-17-keto-marcfortine A (5 mg, 0.01mmol) in THF (5 mL) is treated with a solution of Lithium AluminumHydride (1M, 0.03 mL, 0.03 mmol) in THF at 0°. The mixture is stirredfor 0.5 h at 0° after which a solution of NaHCO₃ (10%) is added. Themixture is extracted with CH₂ Cl₂ (2×5 mL). The extracts are combined,dried (MgSO₄), and the solvent evaporated. Preparative thin layerchromatography of the residue on silica gel (1:20 MeOH:CH₂ Cl₂) afforded14α-hydroxy-14α-methylmarcfortine A (2 mg, 40%). The structure of theproduct can be confirmed by NMR spectroscopy and mass spectrometry. HRMS(FAB) M/Z M+H! calculated for C₂₉ H₃₇ N₃ O₅ +H: 508.2811; measured:508.2816.

Preparation of 14-ketomarcfortine A (Formula 16)

A solution of oxalyl chloride (150 μL) in anhydrous CH₂ Cl₂ (20 mL) istreated with DMSO (170 μL) at -78°. The mixture is stirred for 1 h at-78°. A solution of 14α-hydroxymarcfortine A (110 mg) in CH₂ Cl₂ (5 mL)is added dropwise. The reaction mixture is stirred 20 min at -78°.Triethylamine (1 mL) is added to the reaction mixture which is allowedto warm to room temperature during 20 min. The mixture is partitionedbetween 10% Na₂ CO₃ (20 mL) and CH₂ Cl₂ (20 mL). The organic layer isdried (MgSO₄) and concentrated. The residue is subjected to silica gelchromatography (1:25 MeOH:CH₂ Cl₂) to give 14-ketomarcfortine A (82 mg,75%) as a white solid. The structure of the product can be confirmed byNMR spectroscopy and mass spectrometry. HRMS (FAB) M/Z M+H! calculatedfor C₂₈ H₃₃ N₃ O₅ +H: 492.2498; measured: 492.2510.

EXAMPLE 3

Preparation of 14β-hydroxymarcfortine A (Formula 17)

A solution of 14-ketomarcfortine A (10 mg) in MeOH (2 mL) is treatedwith Sodium borohydride (5 mg) at 0°. The mixture is stirred for 0.5 hat 0° after which a solution of NaHCO₃ (10%) is added. The mixture isextracted with CH₂ Cl₂ (2×10 mL). The extracts are combined, dried(MgSO₄), and the solvent evaporated. Preparative thin layerchromatography of the residue on silica gel (1:16 MeOH:EtOAc) affords14β-hydroxymarcfortine A (5 mg, 50%). The structure of the product canbe confirmed by NMR spectroscopy and mass spectrometry. HRMS (FAB) M/ZM+H! calculated for C₂₈ H₃₅ N₃ O₅ +H: 494.2655; measured: 494.2653.

EXAMPLE 4

Preparation of 14α-hydroxymarcfortine A N-oxide (Formula 18)

A solution of 14α-hydroxymarcfortine A (15 mg) in CH₂ Cl₂ (3 mL) istreated with m-chloroperoxybenzoic acid (15 mg) at 0°. After the mixtureis stirred for 0.5 h at 0°, treated with triethyl amine (30 μL) andconcentrated. Preparative thin layer chromatography of the residue onsilica gel (1:8 MeOH:CH₂ Cl₂) affords 14α-hydroxymarcfortine A N-oxide(12 mg, 80%). The structure of the product can be confirmed by massspectrometry. HRMS (FAB) M/Z M+H! calculated for C₂₈ H₃₅ N₃ O₆ +H:510.2604; measured: 510.2615.

EXAMPLE 5

Preparation of 14α-hydroxy-14β-ethylmarcfortine A (Formula 19)

A solution of 14-ketomarcfortine A (25 mg, 0.05 mnmol) in THF(5 mL) at-78° is treated with a solution of ethylmagnesium bromide (3M, 0.15 mL,0.45 mmol) in Et₂ O at -78°. The resulting mixture is stirred for 0.5 hat -78°. The reaction mixture is allowed to warm to room temperatureduring 20 min. The reaction is quenched by adding 10% Na₂ CO₃ (a fewdrops). The mixture was diluted with CH₂ Cl₂ (10 mL), dried (MgSO₄), andconcentrated. The residue is subjected to silica gel chromatography(1:20 MeOH:CH₂ Cl₂) to give 14α-hydroxy-14β-ethylmarcfortine A (10 mg,45%) as a white solid. The structure of the product can be confirmed byNMR spectroscopy and mass spectrometry. HRMS (FAB) M/Z M+H! calculatedfor C₃₀ H₃₉ N₃ O₅ +H: 522.2968; measured: 522.2983.

Preparation of 14β-methylmarcfortine A from14α-hydroxy-14β-methylmarcfortine A

A solution of potassium bis(trimethylsilyl)amide in toluene (0.5M, 1 mL,0.5 mmol) is added dropwise to a solution of14α(-hydroxy-14β-methylmarcfortine A (66 mg, 0.14 mmol) in THF (2 mL) at-78°. The resulting pale yellow, turbid solution is allowed to warm to-40° during 1 h. The reaction mixture is cooled -78°, stirred 15 min,and then treated by the dropwise addition of a solution ofphenylchlorothionoformate (0.094 mL, 0.7 mmol) in THF (2 mL). After 10min the dry ice bath is removed. After further reaction for 3 h, thereaction is quenched by adding NaHCO₃. The mixture is extracted with CH₂Cl₂ (2×25 mL). The extracts are combined, dried (MgSO₄), andconcentrated to give crude material. This is purified by preparativethin layer chromatography (silica gel, EtOAc) to give14α-O-phenoxythiocarbonyl-14β-methylmarcfortine A.

To a solution of 14α-O-phenoxythiocarbonyl-14β-methylmarcfortine A (64mg, 0.1 mmol) in toluene (5 mL) is added AIBN (3.3 mg) followed byaddition of tributyltin hydride (54 μL, 0.2 mmol). The mixture isrefluxed for 3 h. After the solvent is evaporated, the residue ispurified by preparative thin layer chromatography (silica gel, EtOAc) togive 14β-methylmarcfortine A. The structure can be confirmed by nuclearmagnetic resonance spectroscopy and mass spectrometry.

An alternative synthesis of 17-ketomarcfortine A (Formula 7, Chart E)

To marcfortine A (65 g, 0.136 mol) and sodium bicarbonate (137 g, 1.63mol) in tetrahydrofuran (THF, 2 L) and water (1.25 L) at reflux is addediodine (206 g, 0.81 mol) dropwise in THF (1.25 l) over a one hourperiod. (Alternatively, the mixture can be stirred at room temperaturefor 16 hours.) After being allowed to slowly cool to ambient temperature(2.5 h), the reaction is quenched with saturated sodium thiosulfate (Na₂S₂ O₃, 1.5 L) and extracted with ethyl acetate (2×1 L). The combinedorganic layers are washed with saturated sodium thiosulfate (1 L), dried(MgSO₄), filtered, evaporated and dried overnight in the vacuum oven(65° C.) to give 62 g of crude 17-ketomarcfortine A (Formula 7) as ayellow solid. ¹ H NMR (300 MHz, CDCl₃): δ 7.68 (s, 1H), 6.80 (d, 1H),6.70 (d, 1H), 6.32 (d, 1H), 4.90 (d, 1H), 3.75 (q, 2H), 3.23 (t, 1H),3.09 (s, 3H), 2.80 (d, 1H), 2.65 (d, 1H), 2.49-2.21(m, 2H), 2.08 (d,1H), 1.98-1.45 (m, 5H), 1.46 (s, 3H), 1.44 (s, 3H), 1.09 (s, 3H), 0.90(s, 3H).

Alternatively, ICl can be used instead of iodine.

Synthesis of 16-dithiophenyl-17-ketomarcfortine A (Formula 20)

The crude 17-ketomarcfortine A (5 g, 10.2 mmol) is added via a cannulain THF (150 mL) at -78° C. to an LDA solution which was prepared byadding n-BuLi (1.6M, 24.8 mL, 0.04 mol) dropwise to diisopropyl anine(5.7 mL, 0.041 mol) at 0° C. in THF (100 mL). The reaction mixture isallowed to slowly warm to -50° C. over one hour. The resulting turbidred-brown mixture is then treated with phenyl disulfide (4.4 g, 0.02mol). The reaction is immediately quenched with saturated sodiumbicarbonate solution (100 mL) and extracted with methylene chloride (CH₂Cl₂, 300 mL). The organic phase was dried (MgSO₄), concentrated (8 g),and chromatographed on silica gel (120 g, 60% ethyl acetate/hexane aseluant) to yield the the title compound as an off white solid (4.4 g,61% from marcfortine A). FAB-MS 708 (M⁺ +H); ¹ H NMR (300 MHz, CDCl₃) δ7.74 (s, 1H), 7.71 (d, 2H), 7.64 (d, 2H), 7.45-7.30 (m, 6H), 6.81 (d,1H), 6.72 (d, 1H), 6.32 (d, 1H), 4.91 (d, 1H), 3.70 (q, 2H), 3.16 (t,1H), 3.01 (s, 3H), 2.75 (d, 1H), 2.53 (dt, 1H), 2.35 (dt, 1H), 2.15-1.50(m, 5H), 1.47 (s, 3H), 1.45 (s, 3H), 1.06 (s, 3H), 0.82 (s, 3H).

Synthesis of 16-thiophenyl-16-sulfoxyphenyl-17-ketomarcfortine A(Formula 21)

To 16-dithiophenyl-17-ketomarcfortine A (10 g, 14 mmol) in CH₂ Cl₂ (250mL) at -78° C. under a nitrogen atmosphere is addedm-chloroperoxybenzoic acid (m-CPBA, 64 %, 4.2 g, 15.5 mmol) dropwise inCH₂ Cl₂ (200 mL) for 15 minutes. The reaction is immediately quenchedwith saturated sodium thiosulfate (200 mL), diluted with saturatedNaHCO₃ (200 mL), and extracted into CH₂ Cl₂ (200 mL). Drying (MgSO₄),followed by concentration under reduced pressure gives of 11 g of crude16-thiophenyl-16-sulfoxyphenyl-17-ketomarcfortine A (Formula 21). ¹ HNMR (300 MHz, CDCl₃) δ 8.0-7.29 (m, 11H), 6.80 (d, 1H), 6.70 (d, 1H),6.31 (d, 1H), 4.90 (d, 1H) 3.68 (d, 1H), 3.41 (d, 1H), 3.14 (t, 1H),3.07 (s, 3H), 2.82 (dt, 1H), 2.80-2.65 (m, 2H), 2.16 (dt, 1H), 2.05-1.1(m, 4H), 1.47 (s, 3H), 1.43 (s, 3H), 0.96 (s, 3H), 0.83 (s, 3H).

Synthesis of 16-thiophenyl-15,16-dehydro-17-ketomarcfortine A (Formula22)

The crude 16-thiophenyl-16-sulfoxyphenyl-17-ketomarcfortine A (Formula21, 11 g) is refluxed in toluene (250 mL) for 45 minutes, cooled to roomtemperature, diluted with saturated sodium bicarbonate (300 mL) andextracted with EtOAc (300 mL). The organic layer is dried (MgSO₄) andconcentrated to give 10.6 g of crude16-thiophenyl-15,16-dehydro-17-ketomarcfortine A (Formula 22). FAB-MS598(M⁺ +H); HRMS M/Z (M⁺ +H, C₃₄ H₃₅ N₃ O₅ S+H₁), calc. 598.2376, obsd.598.2387. ¹ H NMR (300 MHz, CDCl₃) 8.18 (s. 1H), 7.55-7.45 (m, 2H),7.29-7.45 (m, 3H), 6.83 (d, 1H), 6.70 (d, 1H), 6.34 (d, 1H), 5.92 (dt,1H), 4.91 (d, 1H), 3.87 (q, 2H), 3.30 (dd, 1H), 3.21 (t, 1H), 3.08 (s,3H), 2.80 (d, 1H), 2.35 (dd, 1H), 2.10 (d, 1H), 2.03 (dd, 1H), 1.78 (dd,1H), 1.46 (s, 3H), 1.44 (s, 3H), 1.11 (s, 3H), 0.88 (s, 3H).

Synthesis of 16-sulfoxyphenyl-15,16-dehydro-17-ketomarcfortine A(Formula 23)

To the crude 16-thiophenyl-15,16-dehydro-17-ketomarcfortine A (Formula22, 10.6 g) in methylene chloride (300 mL) at -78° C. is added m-CPBA(64%, 2.8 g) dropwise in CH₂ Cl₂ (125 mL). The reaction is quenched withsaturated sodium thiosulfate (300 mL) and saturated sodium bicarbonate(300 mL), then extracted into methylene chloride (300 mL). The organiclayer is dried (MgSO₄), filtered and concentrated to give 13 g of crude16-sulfoxyphenyl-15,16-dehydro-17-ketomarcfortine A (Formula 23). ¹ HNMR (300 MHz, CDCl₃) 7.75-7.3 (m, 5H), 6.81 (s, 1H), 6.75-6.6 (m, 2H),6.31 (d, 1H), 4.90 (d, 1H), 3.78-3.58 (m, 2H), 3.22 (t, 1H), 2.98 (s,3H), 2.88-2.45 (m, 2H), 2.12-1.55 (m, 5H), 1.46 (s, 3H), 1.44 (s, 3H),1.12 (s, 3H), 0.88 (s, 3H).

Synthesis of 14α-hydroxy-15,16-dehydro-17-ketomarcfortine A (Formula 9a)from 16-sulfoxyphenyl- 15,16-dehydro-17-ketomarcfortine A (Formula 23)

To the crude 16-sulfoxyphenyl-15,16-dehydro-17-ketomarcfortine A(Formula 23, 13 g) in aqueous MeOH (10/1, 300 mL) is added diethylamnine (15 mL). After refluxing for 0.5 h the reaction mixture is cooledto room temperature, diluted with water (450 mL), and extracted into CH₂Cl₂ (500 mL). Drying (MgSO₄), followed by concentration and silica gelchromatography (130 g, 30% acetone/CH₂ Cl₂ as eluant) produces14α-hydroxy-15,16-dehydro-17-marcfortine A (Formula 9a, 3.6 g, 50 %yield from 16-dithiophenyl-17-keto marcfortine A) as a white solid.

EXAMPLE 6

Synthesis of 14α-hydroxy-N(1)-morpholinocarbonylmarcfortine A (Formula25)

Potassium hydride (70 mg of a 50% oil dispersion) is added to a solutionof 14α-hydroxymarcfortine A (30 mg) in 3 mL of dry tetrahydrofuran. Thesolution is stirred at room temperature for 1 h then morpholinocarbonylchloride (30 υL) is added. The mixture is stirred at room temperaturefor 1 h then partitioned between 5% aqueous sodium bicarbonate (3 mL)and methylene chloride (3 mL). The layers are separated and the aqueouslayer extracted with methylene chloride (3 mL). The combined extractsare dried with magnesium sulfate, filtered, and evaporated under vacuum.Preparative layer chromatography of the residue on a silica gel plateeluted with 5% methanol in methylene chloride affords14α-hydroxy-N(1)-morpholinocarbonylmarcfortine A (15 mg). HRMS (FAB) M/ZM+H! calculated for C₃₃ H₄₂ N₄ O₇ +H: 607.3132; measured: 607.3153

EXAMPLE 7

Synthesis of 14α-acetoxymarcfortine A (Formula 26)

14α-Hydroxymarcfortine A (50 mg) is dissolved in acetonitrile/methylenechloride (4 mL/2mL). This solution is treated with acetic anhydride (50μL), triethyl amine (50 μL) and 4-dimethylaminopyridine (20 mg). Themiture is refluxed for 1 h and cooled to room tempature. It is stirredat room temperature for 16 h, then partitioned between 5% aqueous sodiumbicarbonate (3 mL) and methylene chloride (3 mL). The layers areseparated and the aqueous layer extracted with methylene chloride (3mL). The combined extracts are dried with magnesium sulfate, filtered,and evaporated under vacuum. Preparative layer chromatography of theresidue on a silica gel plate eluted with 2.5% methanol in methylenechloride affords 14α-acetoxymarcfortine A (30 mg). ¹ H NMR (300 MHz,CDCl₃) 8.70 (s, NH), 6.80 (d, J=8.1 Hz, C₄ --H), 6.68 (d, J=8.1 Hz, C₅--H), 6.37 (d, J=7.7 Hz, C₂₄ --H), 5.44 (t, J=2.5 Hz, C₁₄ --H), 4.92 (d,J=7.7 Hz, C₂₅ --H), 3.75 (d, J=11.8 Hz, 1 C₁₂ --H), 3.12 (s, 3H, N-Me),3.04 (t, J=10.2 Hz, C₂₀ --H), 2.6-2.8 (m, 2H), 2.5-2.1 (m, 3H), 2.16 (s,3H, O-acetyl), 2.0-1.5 (m, 4H), 1.44 (s, 6H, C₂₇ --H & C₂₈ --H), 1.12(s, 3H), 0.88 (s, 3H).

Example 8. Synthesis of 14α-O-ethoxycarbonylaminocarbonylmarcfortine A(Formula 27)

14α-Hydroxymarcfortine A (33 mg) is dissolved in acetonitrile/methylenechloride (2 mL/1 mL). This solution is treated with ethoxycarbonylisocyanate (30 μL). The mixture is stirred at room temperature for 1 h,then concentrated. Preparative layer chromatography of the residue on asilica gel plate eluted with 5% methanol in methylene chloride affords14α-ehtoxycarbonylaminocarbonylmarcfortine A (25 mg). ¹ H NMR (300 MHz,CDCl₃) 8.80 (br, 1H, NH), 7.50 (s, NH), 6.80 (d, J=8.1 Hz, C₄ --H), 6.68(d, J=8.1 Hz, C₅ --H), 6.37 (d, J=7.7 Hz, C₂₄ --H), 5.42 (t, J=2.5 Hz,C₁₄ --H), 4.92 (d, J=7.7 Hz, C₂₅ --H), 4.24 (q, 2H, J=7.1 Hz, O-CH₂),3.72 (d, J=11.8 Hz, 1 C₁₂ --H), 3.13 (s, 3H, N-Me), 3.08 (t, J=10.2 Hz,C₂₀ --H), 2.6-2.8 (m, 2H), 2.5-2.1 (m, 5H), 2.0-1.5 (m, 5H), 1.44 (s,6H, C₂₇ --H & C₂₈ --H), 1.28 (t, 3H, J=7.1 Hz, OCH₂ -CH₃), 1.12 (s, 3H),0.88 (s, 3H).

EXAMPLE 9

Synthesis of 14α-hydroxy-N(1)-acetylmarcfortine A (Formula 28)

Potassium hydride (70 mg of a 50% oil dispersion) is added to a solutionof 14α-hydroxymarcfortine A (40 mg) in 3 mL of dry tetrahydrofuran. Thesolution is stirred at room temperature for 1 h then actic anhydride (50μL) is added. The mixture is stirred at room temperature for 1 h thenpartitioned between 5% aqueous sodium bicarbonate (3 mL) and methylenechloride (3 mL). The layers are separated and the aqueous layerextracted with methylene chloride (3 mL). The combined extracts aredried with magnesium sulfate, filtered, and evaporated under vacuum.Preparative layer chromatography of the residue on a silica gel plateeluted with 5% methanol in methylene chloride affords14α-hydroxy-N(1)-acetylmarcfortine A (10 mg). ¹ H NMR (300 MHz, CDCl₃) δ6.88 (q, J 8.1 Hz, C₄ --H & C₅ --H), 6.37 (d, J=7.7 Hz, C₂₄ --H), 4.09(br, C₁₄ --H), 4.86 (d, J =7.7 Hz, C₂₅ --H), 3.23 (d, J =11.3 Hz, 1 C₁₂--H), 3.11 (s, 3H, N-Me), 3.0-1.5 (m, 12H), 2.61 (s, 3H, N-acetyl), 1.44& 1.46 (2s, 6H, C₂₇ --H & C₂₈ --H), 1.08 (s, 3H), 0.82 (s, 3H).

EXAMPLE 10

Synthesis of 14α-O-(10-undecenoyl)marcfortine A (Formula 29)

14α-Hydroxymarcfortine A (33 mg) is dissolved in acetonitrile/methylenechloride (4 mL/2mL). This solution is treated with 10-undecenoylchloride (40 μL), triethyl amine (40 μL) and 4-dimethylaminopyridine (18mg). The miture is refluxed for 16 h and cooled to room tempature. It isthen partitioned between 5% aqueous sodium bicarbonate (3 mL) andmethylene chloride (3 mL). The layers are separated and the aqueouslayer extracted with methylene chloride (3 mL). The combined extractsare dried with magnesium sulfate, filtered, and evaporated under vacuum.Preparative layer chromatography of the residue on a silica gel plateeluted with 5% methanol in methylene chloride affords14α-O-(10-undecenoyl)marcfortine A (7 mg). ¹ H NMR (300 MHz, CDCl₃) δ 88.42 (s, NH), 6.80 (d, J=8.1 Hz, C₄ --H), 6.68 (d, J=8.1 Hz, C₅ --H),6.35 (d, J=7.7 Hz, C₂₄ --H), 5.78 (m, 1H), 5.44 (br, C₁₄ --H), 4.89-5.0(m, 3H), 3.74 (d, J=11.8 Hz, 1 C₁₂ --H), 3.12 (s, 3H, N--Me), 3.05 (t,J=10.2 Hz, C₂₀ --H), 2.6-2.8 (m, 2H), 2.9-1.2 (m, 28H), 1.44 (s, 6H, C₂₇--H & C₂₈ --H), 1.11 (s, 3H), 0.82 (s, 3H).

EXAMPLE 11

Preparation of 14α-hydroxy-14β-vinylmarcfortine A (Formula 30)

A solution of 14-ketomarcfortine A (200 mg, 0.4 mmol) in THF (5 mL) at-78° is treated with a solution of vinylmagnesium bromide (1M, 4.0 mL, 4mmol) in THF at -78°. The resulting mixture is stirred for 2 h at -78°and warmed to room temperature. It is stirred at room temperature for2h. The reaction is quenched by adding 10% Na₂ CO₃ (3 mL). The mixturewas diluted with CH₂ Cl₂ (30 mL), washed with saturated ammoniumchloride solution, dried (MgSO₄), and concentrated. The residue issubjected to silica gel chromatography (6:4 hexane:acetone) to give14α-hydroxy-14β-vinylmarcfortine A (120 mg, 60%, R_(f) =0.45) as a whitesolid. ¹ H NMR (300 MHz, CDCl₃) δ 7.86 (s, NH), 6.78 & 6.67 (d, J=8.1Hz, C₄ --H & C₅ --H), 6.32 (d, J=7.7 Hz, C₂₄ --H), 6.58 (dd, J=17.4,10.9 Hz, 1H, vinyl), 5.43 (d, J=17.4 Hz, 1H, vinyl), 5.18 (d, J=10.9 Hz,1H, vinyl), 4.89 (d, J=7.7 Hz, C₂₅ --H), 3.7 (br, 1H), 3.11 (s, 3H,N--Me), 2.95 (t, 1H, C₂₀ --H), 2.8-1.5 (m, 12H), 1.44 (s, 6H, C₂₇ --H &C₂₈ --H), 1.08 (s, 3H), 0.82 (s, 3H). MS (FAB) M/Z M+H!: 520

EXAMPLE 12

Synthesis of 14α-O-morpholinocarbonyl-N(1)-morpholinocarbonylmarcfortineA (Formula 31)

Potassium hydride (50 mg of a 50% oil dispersion) is added to a solutionof 14α-hydroxymarcfortine A (25 mg) in 3 mL of dry tetrahydrofuran. Thesolution is stirred at room temperature for 1 h then actic anhydride (30μL) is added. The mixture is stirred at room temperature for 3 h thenpartitioned between 5% aqueous sodium bicarbonate (3 mL) and methylenechloride (3 mL). The layers are separated and the aqueous layerextracted with methylene chloride (3 mL). The combined extracts aredried with magnesium sulfate, filtered, and evaporated under vacuum.Preparative layer chromatography of the residue on a silica gel plateeluted with 5% methanol in methylene chloride affords14α-O-morpholninocarbonyl-N(1)-morpholinocarbonylmarcfortine A (17 mg).¹ H NMR (300 MHz, CDCl₃) δ 6.84 (q, J=8.1 Hz, C₄ --H & C₅ --H), 6.41 (d,J=7.7 Hz, C₂₄ --H), 3.8-3.2 (m, 17H), 2.98 (s, 3H, N--Me), 3.0-1.5 (m,13H), 1.45 (s, 6H, C₂₇ --H & C₂₈ --H), 1.41 (s, 3H, C₁₄ --Me), 1.18 (s,3H), 0.83 (s, 3H).

EXAMPLE 13

Preparation of 14α-hydroxy-14β-methylmarcfortine A N-oxide (Formula 32)

A solution of 14α-hydroxymarcfortine A (30 mg) in CH₂ Cl₂ (3 mL) istreated with m-chloroperoxybenzoic acid (20 mg) at 0°. After the mixtureis stirred for 0.5 h, then partitioned between 5% aqueous sodiumbicarbonate (10 mL) and methylene chloride (20 mL). The layers areseparated and the aqueous layer extracted with methylene chloride (10mL). The combined extracts are dried with magnesium sulfate, filtered,and evaporated under vacuum at 0°, treated with triethyl amine (30 μL)and concentrated to produce the title compound as a solid (20 mg). ¹ HNMR (300 MHz, CD₃ OD) δ 6.91 & 6.70 (d, J=8.1 Hz, C₄ --H & C₅ --H), 6.36(d, J=7.7 Hz, C₂₄ --H), 4.91 (d, J=7.7 Hz, C₂₅ --H), 4.08 & 3.76 (AB q,J=12.9 Hz, 2H, C₁₂ --H), 3.5-3.1 (m, 4H), 3.12 (s, 3H, N--Me), 2.8-1.6(m, 7H), 1.46 & 1.44 (2s, 6H, C₂₇ --H & C₂₈ --H), 1.50 (s, 3H, C₁₄--Me), 1.20 (s, 3H), 0.93 (s, 3H).

EXAMPLE 14

Synthesis of 14α-hydroxy-14β-methyl-N(1)-acetylmarcfortine A (Formula33)

Potassium hydride (50 mg of a 50% oil dispersion) is added to a solutionof 14α-hydroxy-14β-methylmarcfortine A (25 mg) in 3 mL of drytetrahydrofuran. The solution is stirred at room temperature for 1 hthen actic anhydride (50 μL) is added. The mixture is stirred at roomtemperature for 1 h then partitioned between 5% aqueous sodiumbicarbonate (3 mL) and methylene chloride (3 mL). The layers areseparated and the aqueous layer extracted with methylene chloride (3mL). The combined extracts are dried with magnesium sulfate, filtered,and evaporated under vacuum. Preparative layer chromatography of theresidue on a silica gel plate eluted with 5% methanol in methylenechloride affords 14α-hydroxy-14β-methyl-N(1)-acetylmarcfortine A (20mg). ¹ H NMR (300 MHz, CDCl₃) δ 6.88 (q, J=8.1 Hz, C₄ --H & C₅ --H),6.37 (d, J=7.7 Hz, C₂₄ --H), 4.86 (d, J=7.7 Hz, C₂₅ --H), 3.68 (d, 1 C₁₂--H), 3.11 (s, 3H, N--Me), 2.9-2.7 (m, 2H), 2.61 (s, 3H, N-acetyl), 2.5-1.5 (m, 10H), 1.47 & 1.46 (2s, 6H, C₂₇ --H & C₂₈ --H), 1.50 (s, 3H, C₁₄--Me), 1.08 (s, 3H), 0.82 (s, 3H).

Preparation of 14α-hydroxy-15α-methyl-17-ketomarcfortine A (Formula 34)

A solution of 14α-hydroxy-15,16-dehydro-17-ketomarcfortine A (Formula9a, 300 mg) in THF (12 mL) is treated with a solution of methylmagnesiumbromide (3M, 1.0 mL, 5 equiv.) at room temperature. The resultingmixture is refluxed for 1.5 h then cooled to room temperature. Thereaction is quenched by adding saturated ammonium chloride (3 mL). Themixture was diluted with CH₂ Cl₂ (30 mL), washed with saturated ammoniumchloride solution, dried (MgSO₄), and concentrated. The residue issubjected to silica gel chromatography (1:20 meOH:methylene chloride) togive 14α-hydroxy-15α-methylmarcfortine A (90 mg, 30%) as a white solid.¹ H NMR (300 MHz, CDCl₃) δ 7.90 (s, NH), 6.80 & 6.70 (d, J=8.1 Hz, C₄--H & C₅ --H), 6.32 (d, J=7.7 Hz, C₂₄ --H), 4.89 (d, J=7.7 Hz, C₂₅ --H),4.36 (br, 1H, C₁₄ --H), 3.74 (br, 2H, C₁₂ --H), 3.20 (t, 1H, C₂₀ --H),3.06 (s, 3H, N--Me), 2.78 & 2.10 (d, 2H, J=15.8 Hz, C₁₀ --H), 2.5-1.8(m, 5H), 1.46 & 1.44 (2s, 6H, C₂₇ --H & C₂₈ --H), 1.13 (d, 3H, C₁₅--Me), 1.12 (s, 3H), 0.88 (s, 3H).

Alternatively, the title compound can be prepared by using lithiumdimethyl cuprate reagent. To copper iodide (0.4 g, 0.002 mol) in THF at0° C. is added methyl lithium (1.4M, 9 mL, 0.013 mol) dropwise. Theresulting pale yellow mixture is stirred for 15 minuties then treateddropwise with 14α-hydroxy-15,16-dehydro-17-ketomarcfortine A (Formula9a, 0.5 g, 0.001 mol) in THF (12 mL) at 0° C. Following 15 minutes ofstirring the turbid orange mixture is quenched with saturated ammoniumchloride (25 mL) and extracted into EtOAc (30 ML). The organic extractwas dried (MgSO4), filtered, and concentrated to give crude materialwhich was purified by a chromatotron (4 mm plate, 4% MeOH/CH₂ Cl₂) toyield product (0.23 g, 44%) as a white solid.

EXAMPLE 15

Preparation of 14α-hydroxy-15α-methylmarcfortine A (Formula 35)

14α-Hydroxy-15α-methyl-17-ketomarcfortine A (90 mg, 0.18 mmol) isdissolved in THF (10 mL) and treated with borane dimethyl sulfidecomplex (12M, 0.18 mL) at 0°. The mixture is stirred for 2 h at 0°, thenMeOH (0.4 mL) is added and stirred for an additional 1 h. After thesolvent is evaporated, the residue is subjected to silica gelchromatography (30:70 acetone:methylene chloride) to give14α-hydroxy-15α-methylmarcfortine A (20 mg) as a solid. ¹ H NMR (300MHz, CDCl₃) δ 8.39 (s, NH), 6.79 & 6.70 (d, J=8.1 Hz, C₄ --H & C₅ --H),6.36 (d, J=7.7 Hz, C₂₄ --H), 4.91 (d, J=7.7 Hz, C₂₅ --H), 3.81 (br, 1H,C₁₄ --H), 3.67 (d, 1H, J=11.7 Hz, C₁₂ --H), 3.03 (t, 1H, C₂₀ --H), 3.11(s, 3H, N--Me), 2.68 & 1.86 (d, 2H, J=15.7 Hz, C₁₀ --H), 2.7-1.2 (m,8H), 1.44 (2s, 6H, C₂₇ --H & C₂₈ --H), 1.02 (d, 3H, J=6.8 Hz, C₁₅ --Me),1.11 (s, 3H), 0.85 (s, 3H). HRMS (FAB) M/Z M+H! calculated for C₂₉ H₃₇N₃ O₅ +H: 508.2811; measured: 508.2840

Preparation of 14,17-diketo-15α-methylmarcfortine A (Formula 36)

A solution of oxalyl chloride (40 μL) in anhydrous CH₂ Cl₂ (5 mL) istreated with DMSO (45 μL) at -78°. The mixture is stirred for 1 h at-78°. A solution of 14α-hydroxy-15α-methyl-17-ketomarcfortine A (27 mg)in CH₂ Cl₂ (2 mL) is added dropwise. The reaction mixture is stirred 20min at -78°. Triethylamine (0.3 mL) is added to the reaction mixturewhich is allowed to warm to room temperature during 20 min. The mixtureis partitioned between 10% Na₂ CO₃ (10 mL) and CH₂ Cl₂ (10 mL). Theorganic layer is dried (MgSO₄) and concentrated. The residue issubjected to silica gel chromatography (1:20 MeOH:CH₂ Cl₂) to give14,17-Diketomarcfortine A (22 mg, 80%) as a white solid. The structureof the product can be confirmed by NMR spectroscopy and massspectrometry. HRMS (FAB) M/Z M+H! calculated for C₂₈ H₃₁ N₃ O₆ +H:506.2291; measured: 506.2280.

Preparation of 14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine A(Formula 37)

A solution of 14,17-Diketo-15α-methylmarcfortine A (25 mg, 0.05 mmol) inCH₂ Cl₂ (5 mL) at -78° is treated with a solution of methylmagnesiumbromide (3 M, 0.2 mL, 0.6 mmol) in Et₂ O at -78°. The resulting mixtureis stirred for 0.5 h at -78°. The reaction is quenched by adding 10% Na₂CO₃ (a few drops). The mixture was diluted with CH₂ Cl₂ (10 mL), dried(MgSO₄), and concentrated. The residue is subjected to silica gelchromatography (1:25 MeOH:CH₂ Cl₂) to give14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine A (16 mg, 62%) as awhite solid. ¹ H NMR (300 MHz, CDCl₃) δ 8.13 (s, 1H), 6.78 (d, 1H), 6.70(d, 1H), 6.33 (d, 1H), 4.91 (d, 1H), 3.75 (q, 2H), 3.16 (t, 1H), 3.05(s, 3H), 2.78 (d, 1H), 2.68-2.57 (m, 1H), 2.42-2.0 (m, 6H), 1.64 (s,3H), 1.45 (s, 3H), 1.44 (s, 3H), 1.11 (s, 3H), 1.04 (d, 3H), 0.92 (d,3H).

EXAMPLE 16

Preparation of 14α-hydroxy-14β-methyl-15α-methylmarcfortine A (Formula38)

14α-Hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine A (15 mg, 0.028mmol) is dissolved in THF (10 mL) and treated with borane dimethylsulfide complex (10M, 0.02 mL) at 0°. The mixture is stirred for 2 h at0°, then MeOH (0.4 mL) is added and stirred for an additional 1 h. Afterthe solvent is evaporated, the residue is subjected to silica gelchromatography (30:70 acetone: methylene chloride) to give14α-hydroxy-14β-methyl-15α-methylmarcfortine A (4 mg, 29%) as a solid. ¹H NMR (300 MHz, CDCl₃) δ 7.82 (s, 1H), 6.79 (d, 1H), 6.67 (d, 1H), 6.33(d, 1H), 4.90 (d, 1H), 3.65 (d, 1H), 3.09 (s, 3H), 2.98 (t, 1H), 2.69(d, 1H), 2.60-2..22 (m, 7H), 2.06 (dd, 1H), 1.87 (d, 1H), 1.85-1.75 (m,1H), 1.44 (s, 6H), 1.43 (s, 3H), 1.10 (s, 3H), 0.94 (d, 3H), 0.86(s,3H).

Suitable C-24, C-25, N-1 and N-18a substituted marcfortine A, B, C, andD derivatives for starting materials in the above sequence of reactionsare readily prepared by the procedures given in U.S. Pat. No. 4,923,867.The reactions are conducted in a suitable inert solvent such aspyridine, collidine, toluene (preferred), xylene, dioxane,tetrahydrofuran, and the like, at temperatures from 10° to 180°preferably 80° to 140°.

Alternatively, the C-24, C-25 and N-1 derivatives can be prepared fromthe marcfortines. For example, a large series of marcfortine analogs canbe prepared by alkylation of N-1 of the N-18a substituted marcfortines.These derivatives may be easily prepared by sequential treatment of asolution of marcfortine A, N-18a-substituted marcfortine B, orN-18a-substituted marcfortine C in an aprotic organic solvent such astetrahydrofuran, ether, benzene and the like with an excess of a strongbase such as potassium hydride (preferred), sodium hydride,butyllithium, potassium tert-butoxide, and the like followed by asuitable alkylating agent at temperatures ranging from 0° C. to 50° C.for 0.25 to 48 hours. Suitable alkylating agents include alkyl bromides,alkyl iodides, alkyl sulfonates, alkenyl iodides, alkynyl bromides,alkoxyalkyl chlorides, and the like.

An additional series of derivatives can be generated by modification ofthe C24-C25 double bond of marcfortines A, B and C. The 24,25-dihydroanalogs are readily prepared by stirring a solution of the appropriatemarcfortine in an alcoholic solvent such as methanol, ethanol, propanoland the like with a catalyst such as palladium, platinum, tris(triphenylphosphine)-chlororhodium and the like in the presence ofhydrogen gas. The product, which is a 24,25-dihydromarcfortine analog,can be isolated and purified by using techniques known to those skilledin the art. Note that the reactions described above for modification ofother portions of the marcfortine structure may also be applied to24,25-dihydro marcfortine analogs to prepare the corresponding24,25-dihydro analogs. Additional G ring modified analogs of themarcfortines may be prepared via the 24,25-dibromide which is easilyprepared by treating a solution of a marcfortine in a halogenatedsolvent such as dichloromethane, chloroform, carbon tetrachloride andthe like with 1 molar equivalent of bromine at temperatures ranging from-20° C. to 25° C. for 0.25 to 8 hours. This process affords thecorresponding 24,25-dibromo 24,25-dihydromarcfortine derivative whichcan be isolated and purified by using techniques known to those skilledin the art. Note that the 24,25-dichloro analog may be prepared bysubstituting chlorine for bromine in the process described above. The24,25-dibromo-24,25-dihydro-marcfortine analogs described above areuseful intermediates for the preparation of additional derivatives.Thus, treatment of a solution of the dibromide in an alcoholic solventsuch as methanol, ethanol, propanol, and the like with a strong basesuch as 1,8-diazabicyclo 5.4.0!undec-7-ene (DBU) at temperatures rangingfrom 0° C. to 30° C. for 0.25 to 24 hours affords 24-alkoxy-25bromo-24,25 dihydro-marcfortine analogs which can be isolated andpurified by using techniques known to those skilled in the art. These24-alkoxy, 25-bromo derivatives can be debrominated by treatment of asolution of the compound in an aprotic organic solvent such as benzene,toluene, hexane, and the like with a tin hydride reducing agent such astributyltin hydride, triphenyltin hydride and the like with or withoutthe addition of a initiator radical such as azobis-isobutyronitrile(AIBN) at temperatures ranging from 25° C. to 120° C. for 0.5 to 48hours. This process affords the corresponding 24-alkoxy-marcfortinederivatives (R₂₄ =lower alkoxy in the general structure) which can beisolated and purified by using techniques known to those skilled in theart.

Haemonchus contortus/Trichostrongylus colubriformis/Jird Assay

This in vivo assay utilizes jirds infected with two important targetparasites of ruminants, H. contortus and T. colubriformis(anthelmintic-sensitive or -resistant worms can be used). Initially,activity is assessed only against H. contortus as described in G. A.Conder et al., J. Parasitol. 76, 168-170 (1990), while follow-up studiesexamine activity against both species of parasites using the techniquesoutlined in G. A. Conder et al., J. Parasitol. 77, 621-623 (1991). Theactivity of 14α-hydroxymarcfortine A, 14α-hydroxy-14β-methylmarcfortineA, 14β-hydroxymarcfortine A, 14α-hydroxymarcfortine A N-oxide, andmarcfortine D is set forth in Table I.

                                      TABLE I                                     __________________________________________________________________________    Percentage Clearance of Haemonchus contortus and Trichostrongylus             colubriformis from                                                            jirds inoculated per os with ˜1,000 exsheathed, infective larvae of     each parasite, treated per os                                                 with testing compounds on day 10 postinoculation (PI) and necropsied on       day 13 post inoculation.                                                      __________________________________________________________________________                                               Percentage Clearance                                            n                                                                        Dose (survived to  H.   T.                            Compound   Purity       (mg/jird)                                                                          necropsy)     contortus                                                                          colubriformis                 __________________________________________________________________________    marcfortine A                                                                            100 %        0.33 3(3)           97-100                                                                             99-100                       marcfortine D                                                                            100%         1.0  3(3)           0    72                           Example 1. 100%         0.11 3(3)           99-100                                                                             99-100                       Example 2. 100%         0.33 3(3)          100  100                           Example 3. 100%         1.0  3(3)           54   41                           Example 4. 100%         0.33 3(3)          100   99                           Example 5. 100%         0.33 3(3)          88-99                                                                               99-100                       Example 6. 100%         0.33 3(3)          100  100                           Example 7. 100%         0.11 3(3)          100  100                           Example 8. 100%         0.33 3(3)          98-99                                                                              100                           Example 9. 100%         0.11 3(3)          100   99                           Example 10.                                                                              100%         0.11 3(3)          98-99                                                                              100                           Example 11.                                                                              100%         0.33 3(3)          92-98                                                                              94-96                         Example 12.                                                                              100%         0.33 3(3)          100   99                           Example 13.                                                                              100%         0.33 3(3)           98-100                                                                            97-99                         Example 14.                                                                              100%         0.33 3(3)           99-100                                                                            100                           Example 15.                                                                              100%         0.11 3(3)           98   99                           Example 16.                                                                              100%         0.33 3(3)           80  100                           __________________________________________________________________________    CHART A                                                                        ##STR12##                                                                     ##STR13##                                                                     ##STR14##                                                                     ##STR15##                                                                    CHART B                                                                        ##STR16##                                                                     ##STR17##                                                                     ##STR18##                                                                    CHART C                                                                        ##STR19##                                                                     ##STR20##                                                                     ##STR21##                                                                    CHART D                                                                        ##STR22##                                                                     ##STR23##                                                                    CHART E                                                                        ##STR24##                                                                     ##STR25##                                                                     ##STR26##                                                                     ##STR27##                                                                    CHART F                                                                        ##STR28##                                                                                                    ##STR29##                                      ##STR30##                                                                                                    ##STR31##                                      ##STR32##                                                                     ##STR33##                                                                     ##STR34##                                                                     ##STR35##                                                                                                    ##STR36##                                     CHART G                                                                        ##STR37##                                                                     ##STR38##                                                                     ##STR39##                                                                

I claim:
 1. A compound of Formula I ##STR40## or a pharmaceuticallyacceptable salt, or 12α-N-oxide thereof; wherein:m is 0 or 1; Z is 0 orS; R₁ is hydrogen, C₁ -C₇ alkyl, cyclo C₃ -C₈ alkyl, benzyl, C₂ -C₇alkanoyl (--C(O)C₂ --C₇ alkyl) {optionally substituted with carboxy(--COOH), C₁ -C₇ alkanoyl, carboC₁ -C₇ alkoxy (--C(O)OC₁ -C₇ alkyl),--NR₄ R₅, aminocarbonyl (--C(O)NR₄ R₅)}, C₁₀ -C₂₄ alkanoyl (--C(O)C₁₀-C₂₄ alkyl, cyclo C₃ -C₈ alkanoyl {optionally substituted with carboxy,C₁ --C₇ alkanoyl, carboC₁ -C₇ alkoxy, --NR₄ R₅, aminocarbonyl},alkanoyloxymethylene (--CH₂ OC(O)-C_(2-C) ₇ alkyl), benzoyloxymethlene(--CH₂ OC(O)phenyl) {optionally substituted with 1 or 2 groups selectedfrom halogen, C₁ -C₄ alkyl, haloC₁ -C₇ alkyl, nitro, cyano and C₁ -C₇alkoxy }, C₁₀ -C₂₄ alkenoyl (--C(O)C₉ -C₂₃ alkenyl), benzenesulfonyl(--SO₂ CH₂ phenyl) {optionally substituted with 1 or 2 groups selectedfrom halogen, C₁ -C₄ alkyl, haloC₁ -C₇ alkyl, nitro, cyano and C₁ -C₇alkoxy}, C₁ -C₄ alkylaminocarbonyl (--C(O)N(C₁ -C₄ alkyl)₂), C₁ -C₄alkylaminothiocarbonyl (--C(S)N(C₁ -C₄ alkyl)₂), C₁ -C₇ alkoxycarbonyl,phenoxycarbonyl {optionally substituted with 1 or 2 groups selected fromhalogen, C₁ -C₄ alkyl, haloC₁ -C₇ alkyl, nitro, cyano and C₁ -C₇alkoxy}, --C(O)NR'₄ R'₅, --P(═X)(R₂)(R₃), --SR₆, --SO₂ NR₄ R5, benzoylsubstituted at the 3 or 4 position with --CH₂ NR₄ R₅ or bicycloC₈ -C₁₂alkanoyl; R₄ and R₅, being the same or different, are selected fromhydrogen, C₁ -C₇ alkyl, phenyl {optionally substituted with 1 or 2groups selected from halogen, C₁₋₄ alkyl, haloC₁ -C₇ alkyl, nitro, cyanoand C₁ -C₇ alkoxy}; R'₄ and R'₅, being the same or different, areselected from C₁ -C₇ alkyl, cyclo(C₃ -C₈)alkyl, phenyl {optionallysubstituted with 1 or 2 groups selected from halogen, C₁ -₄ alkyl,haloC₁ -C₇ alkyl, nitro, cyano and C₁ -C₇ alkoxy}; X is O or S; R₂ andR₃, being the same or different, are selected from C₁ -C₇ alkyl, phenyl{optionally substituted with 1 or 2 groups selected from halogen, C₁ -₄alkyl, haloC₁ -C₇ alkyl, nitro, cyano and C₁ -C₇ alkoxy}, C₁ -C₇ alkoxy,thio(C₁ -C₇)alkoxy, phenoxy, thiophenoxy, --NR₇ R₈ {where R₇ and R₈,being the same or different, are selected from H or C₁ -C₇ alkyl; R₆ isC₁ -C₇ alkyl, haloC₁ -C₇ alkyl, carboC₁ -C₇ alkoxy, --NR₉ R₁₀ o where R₉and R₁₀, being the same or different, are C₁ -C₇ alkyl or phenyl(optionally substituted with 1 or 2 groups selected from halo, loweralkyl, haloC₁ -C₇ alkyl, nitro, cyano, C₁ -C₇ alkoxy); R₂₄ is hydrogen,halogen or C₁ -C₇ alkoxy; R₂₅ is hydrogen or halogen; R18a is hydrogen,C₁ -C₇ alkyl, C₂ -C₈ alkoxyalkyl, C₂ -C₈ alkenyl, C₂ -C₈ alkynyl orbenzyl; R14a is hydroxyl, hydrogen, C₁ -C₇ alkyl, C₂ -C₈ alkoxyalkyl,cyclo(C₃ -C₈)alkyl or benzyl (optionally substituted with 1 or 2 groupsselected from halo, lower alkyl, haloC₁ -C₇ alkyl, nitro, cyano, C₁ -C₇alkoxy); R_(14b) is hydroxyl, hydrogen, C₁ -C₇ alkoxy, cyclo(C₃-C₈)alkyl or benzoxyl (optionally substituted with 1 or 2 groupsselected from halo, lower alkyl, haloC₁ -C₇ alkyl, nitro, cyano, C₁ -C₇alkoxy); R₁₅ a and R_(15b) are both hydrogen, with the provisio thatwhen one of R_(14a) or R_(14b) is hydroxyl and the other is hydrogen ormethyl, R_(15a) and R_(15b) can be hydrogen or methyl; and with theoverall proviso that R_(14a) and R_(14b) are not both hydrogen.
 2. Acompound according to claim 1 where m is
 0. 3. A compound according toclaim 2 where R₂₄ and R₂₅ are hydrogen; and R_(18a) is hydrogen, C₁ -C₇alkyl, C₁ -C₈ alkoxymethyl, C₂ -C₈ alkenyl or benzyl.
 4. A compoundaccording to claim 1 where Z is an oxygen atom.
 5. A compound accordingto claim 4 where R₂₄ and R₂₅ are hydrogen; and R_(18a) is hydrogen, C₁-C₇ alkyl, C₁ -C₈ alkoxymethyl, C₂ -C₈ alkenyl or benzyl.
 6. A compoundaccording to claim 1 where Z is a sulfur atom.
 7. A compound accordingto claim 6 where R₂₄ and R₂₅ are hydrogen; and R_(18a) is hydrogen, C₁-C₇ alkyl, C₁ -C₈ alkoxymethyl, C₂ -C₈ alkenyl or benzyl.
 8. A compoundwhich is selected from the group consistingof1-acetoxymethyl-14α-hydroxymarcfortine A;1-diethoxyphosphoryl-14α-hydroxymarcfortine A;1-dimethylsulfamoyl-14α-hydroxymarcfortine A;1-cyclopropylcarbonyl-14α-hydroxymarcfortine A; 2-bicyclo2.2.1!heptanoyl-14α-hydroxymarcfortine A;1-succinoyl-14α-hydroxymarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxymarcfortine A;1-(p-toluenesulfonyl)-14α-hydroxymarcfortine A;1-acetyl-14α-hydroxymarcfortine A; 1-methyl-14α-hydroxymarcfortine A;1-benzyl-14α-hydroxymarcfortine A;1-dimethylcarbamoyl-14α-hydroxymarcfortine A;1-methoxycarbonyl-14α-hydroxymarcfortine A; 14α-hydroxymarcfortine B;1-(p-toluenesulfonyl)-14α-hydroxymarcfortine B;1-ethyl-14α-hydroxymarcfortine B; 1-benzyl-14α-hydroxymarcfortine B;18a-ethyl-14α-hydroxymarcfortine B; 18a-benzyl-14α-hydroxymarcfortine B;18a-methoxyethoxymethyl-14α-hydroxymarcfortine B;18a-allyl-14α-hydroxymarcfortine B; 18a-propargyl-14α-hydroxymarcfortineB; 1,18a-bis-ethyl-14α-hydroxymarcfortine B; 1,18a-bis-benzyl-14-hydroxymarcfortine B; 18a-ethyl-24-methoxy-14α-hydroxymarcfortine B;1-palmitoyl-14α-hydroxymarcfortine A;1-acetoxymethyl-14α-hydroxy-14β-methylmarcfortine A;1-diethoxyphosphoryl-14α-hydroxy-14β-methylmarcfortine A;1-dimethylsulfamoyl-14α-hydroxy-14β-methylmarcfortine A;1-cyclopropylcarbonyl-14α-hydroxy-14β-methylmarcfortine A; 2-bicyclo2.2.1!heptanoyl-14α-hydroxy-14β-methylmarcfortine A;1-succinoyl-14α-hydroxy-14β-methylmarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-14β-methylmarcfortine A;1-(p-toluenesulfonyl)-14α-hydroxy-14β-methylmarcfortine A;1-acetyl-14α-hydroxy-14β-methylmarcfortine A;1-methyl-14α-hydroxy-14β-methylmarcfortine A;1-benzyl-14α-hydroxy-14β-methylmarcfortine A;1-dimethylcarbamoyl-14α-hydroxy-14β-methylmarcfortine A;1-methoxycarbonyl-14α-hydroxy-14β-methylmarcfortine A;14α-hydroxy-14β-methylmarcfortine B;1-(p-toluenesulfonyl)-14α-hydroxy-14β-methylmarcfortine B;1-ethyl-14α-hydroxy-14β-methylmarcfortine B;1-benzyl-14α-hydroxy-14β-methylmarcfortine B;18a-ethyl-14α-hydroxy-14β-methylmarcfortine B;18a-benzyl-14α-hydroxy-14β-methylmarcfortine B;18a-methoxyethoxymethyl-14α-hydroxy-14β-methylmarcfortine B; 1α-allyl-14α-hydroxy-14β-methylmarcfortine B;18a-propargyl-14α-hydroxy-14β-methylmarcfortine B;1,18a-bis-ethyl-14α-hydroxy-14β-methylmarcfortine B;1,18a-bis-benzyl-14α-hydroxy-14β-methylmarcfortine B;18a-ethyl-24-methoxy-14α-hydroxy-14β-methylmarcfortine B;1-palmitoyl-14α-hydroxy-1 4β-methylmarcfortine A;1-acetoxymethyl-14α-hydroxy-14β-ethylmarcfortine A;1-diethoxyphosphoryl-14α-hydroxy-14β-ethylmarcfortine A;1-dimethylsulfamoyl-14α-hydroxy-14β-ethylmarcfortine A;1-cyclopropylcarbonyl-14α-hydroxy-14β-ethylmarcfortine A; 2-bicyclo2.2.1!heptanoyl-14α-hydroxy-14β-ethylmarcfortine A;1-succinoyl-14α-hydroxy-14β-ethylmarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-14β-ethylmarcfortine A;1-(p-toluenesulfonyl)-14α-hydroxy-14β-ethylmarcfortine A;1-acetyl-14α-hydroxy-14β-ethylmarcfortine A;1-methyl-14α-hydroxy-14β-ethylmarcfortine A;1-benzyl-14α-hydroxy-14β-ethylmarcfortine A;1-dimethylcarbamoyl-14α-hydroxy-14β-ethylmarcfortine A;1-methoxycarbonyl-14α-hydroxy-14β-ethylmarcfortine A;14α-hydroxy-14β-ethylmarcfortine B;1-(p-toluenesulfonyl)-14α-hydroxy-14β-ethylmarcfortine B;1-ethyl-14α-hydroxy-14β-ethylmarcfortine B;1-benzyl-14α-hydroxy-14β-ethylmarcfortine B;18a-ethyl-14α-hydroxy-14β-ethylmarcfortine B;18a-benzyl-14α-hydroxy-14β-ethylmarcfortine B;18a-methoxyethoxymethyl-14α-hydroxy-14β-ethylmarcfortine B;18a-allyl-14α-hydroxy-14β-ethylmarcfortine B;18a-propargyl-14α-hydroxy-14β-ethylmarcfortine B;1,18a-bis-ethyl-14α-hydroxy-14β-ethylmarcfortine B;1,18a-bis-benzyl-14α-hydroxy-14β-ethylmarcfortine B;18a-ethyl-24-methoxy-14α-hydroxy-14β-ethylmarcfortine B;1-palmitoyl-14α-hydroxy-14β-ethylmarcfortine A;1-acetoxymethyl-14β-methylmarcfortine A;1-diethoxyphosphoryl-14β-methylmarcfortine A;1-dimethylsulfamoyl-14β-methylmarcfortine A;1-cyclopropylcarbonyl-14β-methylmarcfortine A; 2-bicyclo2.2.1!heptanoyl-14β-methylmarcfortine A;1-succinoyl-14β-methylmarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-14β-methylmarcfortine A;1-(p-toluenesulfonyl)-14β-methylmarcfortine A;1-acetyl-14β-methylmarcfortine A; 1-methyl-14β-methylmarcfortine A;1-benzyl-14β-methylmarcfortine A;1-dimethylcarbamoyl-14β-methylmarcfortine A;1-methoxycarbonyl-14β-methylmarcfortine A; 14β-methylmarcfortine B;1-(p-toluenesulfonyl)-14β-methylmarcfortine B; 1-ethyl-14β-methylmarcfortine B; 1-benzyl-14β-methylmarcfortine B;18a-ethyl-14β-methylmarcfortine B; 18a-benzyl-14β-methylmarcfortine B;18a-methoxyethoxymethyl-14β-methylmarcfortine B;18a-allyl-14β-methylmarcfortine B; 18a-propargyl-14β-methylmarcfortineB; 1,18a-bis-ethyl-14β-methylmarcfortine B;1,18a-bis-benzyl-14β-methylmarcfortine B;18a-ethyl-24-methoxy-14β-methylmarcfortine B;1-palmitoyl-14β-methylmarcfortine A;1-acetoxymethyl-14β-ethylmarcfortine A;1-diethoxyphosphoryl-14β-ethylmarcfortine A;1-dimethylsulfamoyl-14β-ethylmarcfortine A;1-cyclopropylcarbonyl-14β-ethylmarcfortine A; 2-bicyclo2.2.1!heptanoyl-14β-ethylmarcfortine A; 1-succinoyl-14β-ethylmarcfortineA; 1-(2,4-dinitrobenzenesulfenyl)-14β-ethylmarcfortine A;1-(p-toluenesulfonyl)-14β-ethylmarcfortine A;1-acetyl-14β-ethylmarcfortine A; 1-methyl-14β-ethylmarcfortine A;1-benzyl-14β-ethylmarcfortine A;1-dimethylcarbamoyl-14β-ethylmarcfortine A;1-methoxycarbonyl-14β-ethylmarcfortine A; 14β-ethylmarcfortine B;1-(p-toluenesulfonyl)-14β-ethylmarcfortine B;1-ethyl-14β-ethylmarcfortine B; 1-benzyl-14β-ethylmarcfortine B;18α-ethyl-14β-ethylmarcfortine B; 18a-benzyl-14β-ethylmarcfortine B;18a-methoxyethoxymethyl-14β-ethylmarcfortine B;18a-allyl-14β-ethylmarcfortine B; 18a-propargyl-14β-ethylmarcfortine B;1,18a-bis-ethyl-14β-ethylmarcfortine B;1,18a-bis-benzyl-14β-ethylmarcfortine B;18a-ethyl-24-methoxy-14β-ethylmarcfortine B;1-palmitoyl-14β-ethylmarcfortine A;1-acetoxymethyl-14α-O-methylmarcfortine A; 14α-O-methylmarcfortine A;14α-O-methyl-14α-methylmarcfortine A; 14α-O-methyl-14α-ethylmarcfortineA; 1-diethoxyphosphoryl-14α-O-methylmarcfortine A;1-dimethylsulfamoyl-14α-O-methylmarcfortine A;1-cyclopropylcarbonyl-14α-O-methylmarcfortine A; 2-bicyclo 2.2.1!heptanoyl-14α-O-methylmarcfortine A;1-succinoyl-14α-O-methylmarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-14α-O-methylmarcfortine A;1-(p-toluenesulfonyl)-14α-O-methylmarcfortine A;1-acetyl-14α-O-methylmarcfortine A; 1-methyl-14α-O-methylmarcfortine A;1-benzyl-14α-O-mehtylmarcfortine A;1-dimethylcarbamoyl-14α-O-methylmarcfortine A;1-methoxycarbonyl-14α-O-methylmarcfortine A; 14α-O-methylmarcfortine B;1-(p-toluenesulfonyl)-14α-O-methylmarcfortine B;1-ethyl-14α-O-methylmarcfortine B; 1-benzyl-14α-O-methylmarcfortine B;18a-ethyl-14α-O-methylmarcfortine B; 18a-benzyl-14α-O-methylmarcfortineB; 18a-methoxyethoxymethyl-14α-O-methylmarcfortine B;18a-allyl-14α-O-methylmarcfortine B;18a-propargyl-14α-O-methylmarcfortine B;1,18a-bis-ethyl-14α-O-methylmarcfortine B;1,18a-bis-benzyl-14α-O-methylmarcfortine B;18a-ethyl-24-methoxy-14α-O-methylmarcfortine B;1-palmitoyl-14α-O-methylmarcfortine A;1-acetoxymethyl-14α-O-methyl-14β-methylmarcfortine A;1-diethoxyphosphoryl-14α-O-methyl-14β-methylmarcfortine A;1-dimethylsulfamoyl-14α-O-methyl-14β-methylmarcfortine A;1-cyclopropylcarbonyl-14α-O-methyl-14β-methylmarcfortine A; 2-bicyclo2.2.1!heptanoyl-14α-O-methyl-14β-methylmarcfortine A;1-succinoyl-14α-O-methyl-14β-methylmarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-14α-O-methyl-14β-methylmarcfortine A;1-(p-toluenesulfonyl)-14α-O-methyl-14β-methylmarcfortine A;1-acetyl-14α-O-methyl-14β-methylmarcfortine A; 1-methyl-14α-O-methyl-14β-methylmarcfortine A;1-benzyl-14α-O-methyl-14β-methylmarcfortine A;1-dimethylcarbamoyl-14α-O-methyl-14β-methylmarcfortine A;1-methoxycarbonyl-14α-O-methyl-14β-methylmarcfortine A;14α-O-methyl-14β-methylmarcfortine B;1-(p-toluenesulfonyl)-14α-O-methyl-14β-methylmarcfortine B;1-ethyl-14α-O-methyl-14β-methylmarcfortine B;1-benzyl-14α-O-methyl-14β-methylmarcfortine B;18a-ethyl-14α-O-methyl-14β-methylmarcfortine B;18a-benzyl-14α-O-methyl-14β-methylmarcfortine B;18a-methoxyethoxymethyl-14α-O-methyl-14β-methylmarcfortine B;18a-allyl-14α-O-methyl-14β-methylmarcfortine B;18a-propargyl-14α-O-methyl-14β-methylmarcfortine B;1,18a-bis-ethyl-14α-O-methyl-14β-methylmarcfortine B;1,18a-bis-benzyl-14α-O-methyl-14β-methylmarcfortine B;1,18a-ethyl-24-methoxy-14α-O-methyl-14β-methylmarcfortine B;1-palmitoyl-14α-O-methyl-14β-methylmarcfortine A;1-acetoxymethyl-14α-O-methyl-14β-ethylmarcfortine A;1-diethoxyphosphoryl-14α-O-methyl-14β-ethylmarcfortine A;1-dimethylsulfamoyl-14α-O-methyl-14β-ethylmarcfortine A;1-cyclopropylcarbonyl-14α-O-methyl-14β-ethylmarcfortine A; 2-bicyclo2.2.1!heptanoyl-14α-O-methyl-14β-ethylmarcfortine A;1-succinoyl-14αα-O-methyl-14β-ethylmarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-14α-O-methyl-14β-ethylmarcfortine A;1-(p-toluenesulfonyl)-14α-O-methyl-14β-ethylmarcfortine A;1-acetyl-14α-O-methyl-14β-ethylmarcfortine A;1-methyl-14α-O-methyl-14β-ethylmarcfortine A;1-benzyl-14α-O-methyl-14β-ethylmarcfortine A;1-dimethylcarbamoyl-14α-O-methl-14β-ethylmarcfortine A;1-methoxycarbonyl-14α-O-methyl-14β-ethylmarcfortine A;14α-O-methyl-14β-ethylmarcfortine B;1-(p-toluenesulfonyl)-14α-O-methyl-14β-ethylmarcfortine B;1-ethyl-14α-O-methyl-14β-ethylmarcfortine B;1-benzyl-14α-O-methyl-14β-ethylmarcfortine B;18a-ethyl-14α-O-methyl-14β-ethylmarcfortine B;18a-benzyl-14α-O-methyl-14β-ethylmarcfortine B;18a-methoxyethoxymethyl-14α-O-methyl-14β-ethylmarcfortine B;18a-allyl-14α-O-methyl-14β-ethylmarcfortine B;18a-propargyl-14α-O-methyl-14β-ethylmarcfortine B;1,18a-bis-ethyl-14α-O-methyl-14β-ethylmarcfortine B;1,18a-bis-benzyl-14α-O-methyl-14β-ethylmarcfortine B;18a-ethyl-24-methoxy-14α-O-methyl-14β-ethylmarcfortine B;1-palmitoyl-14α-O-methyl-14β-ethylmarcfortine A;1-acetoxymethyl-14α-O-allylmarcfortine A; 14α-O-allylmarcfortine A;14α-O-allyl-14β-methylmarcfortine A; 14α-O-allyl-14β-ethylmarcfortine A;1-diethoxyphosphoryl-14α-O-allylmarcfortine A;1-dimethylsulfamoyl-14α-O-allylmarcfortine A;1-cyclopropylcarbonyl-14α-O-allylmarcfortine A; 2-bicyclo2.2.1!heptanoyl-14α-O-allylmarcfortine A;1-succinoyl-14α-O-allylmarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-14α-O-allylmarcfortine A;1-(p-toluenesulfonyl)-14α-O-allylmarcfortine A;1-acetyl-14α-O-allylmarcfortine A; 1-methyl-14α-O-allylmarcfortine A;1-benzyl-14α-O-allylmarcfortine A;1-dimethylcarbamoyl-14α-O-allylmarcfortine A;1-methoxycarbonyl-14α-O-allylmarcfortine A; 14α-O-allylmarcfortine B;1-(p-toluenesulfonyl)-14α-O-allylmarcfortine B;1-ethyl-14α-O-allylmarcfortine B; 1-benzyl-14α-O-allylmarcfortine B;18a-ethyl-14α-O-allylmarcfortine B; 18a-benzyl-14α-O-allylmarcfortine B;18a-methoxyethoxymethyl-14α-O-allylmarcfortine B;18a-allyl-14α-O-allylmarcfortine B; 18a-propargyl-14α-O-allylmarcfortineB; 1,18a-bis-ethyl-14α-O-allylmarcfortine B;1,18a-bis-benzyl-14α-O-allylmarcfortine B;18a-ethyl-24-methoxy-14α-O-allylmarcfortine B;1-palmitoyl-14α-O-allylmarcfortine A;1-acetoxymethyl-14α-O-allyl-14β-methylmarcfortine A;1-diethoxyphosphoryl-14α-O-allyl-14β-methylmarcfortine A;1-dimethylsulfamoyl-14α-O-allyl-14β-methylmarcfortine A;1-cyclopropylcarbonyl-14α-O-allyl-14β-methylmarcfortine A; 2-bicyclo2.2.1!heptanoyl-14α-O-allyl-14β-methylmarcfortine A;1-succinoyl-14α-O-allyl-14β-methylmarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-14α-O-allyl-14β-methylmarcfortine A;1-(p-toluenesulfonyl)-14α-O-allyl-14β-methylmarcfortine A;1-acetyl-14α-O-allyl-14β-methylmarcfortine A;1-methyl-14α-O-allyl-14β-methylmarcfortine A;1-benzyl-14α-O-allyl-14β-methylmarcfortine A;1-dimethylcarbamoyl-14α-O-allyl-14β-methylmarcfortine A;1-methoxycarbonyl-14α-O-allyl-14β-methylmarcfortine A;14α-O-allyl-14β-methylmarcfortine B;1-(p-toluenesulfonyl)-14α-O-allyl-14β-methylmarcfortine B;1-ethyl-14α-O-allyl-14β-methylmarcfortine B;1-benzyl-14α-O-allyl-14β-methylmarcfortine B;18a-ethyl-14α-O-allyl-14β-methylmarcfortine B;18a-benzyl-14α-allyl-14β-methylmarcfortine B;18a-methoxyethoxymethyl-14α-allyl-14β-methylmarcfotine B;18a-allyl-14α-allyl-14β-methylmarcfortine B;18a-propargyl-14α-O-allyl-14β-methylmarcfortine B;1,18a-bis-ethyl-14α-O-allyl-14β-methylmarcfortine B;1,18a-bis-benzyl-14α-O-allyl-14β-methylmarcfortine B;18a-ethyl-24-methoxy-14α-O-allyl-14β-methylmarcfortine B;1-palmitoyl-14α-O-allyl-14β-methylmarcfortine A;1-acetoxymethyl-14α-O-allyl-14β-ethylmarcfortine A;1-diethoxyphosphoryl-14α-O-allyl-14β-ethylmarcfortine A;1-dimethylsulfamoyl-14α-O-allyl-14β-ethylmarcfortine A;1-cyclopropylcarbonyl-14α-O-allyl-14β-ethylmarcfortine A; 2-bicyclo2.2.1!heptanoyl-14α-O-allyl-14β-ethylmarcfortine A;1-succinoyl-14α-O-allyl-14β-ethylmarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-14α-O-allyl-14β-ethylmarcfortine A;1-(p-toluenesulfonyl)-14α-O-allyl-14β-ethylmarcfortine A;1-acetyl-14αα-O-allyl-14β-ethylmarcfortine A;1-methyl-14α-O-allyl-14β-ethylmarcfortine A;1-benzyl-14α-O-allyl-14β-ethylmarcfortine A;1-dimethylcarbamoyl-14α-O-allyl-14β-ethylmarcfortine A;1-methoxycarbonyl-14α-O-allyl-14β-ethylmarcfortine A;14α-O-allyl-14β-ethylmarcfortine B;1-(p-toluenesulfonyl)-14α-O-allyl-14β-ethylmarcfortine B;1-ethyl-14α-O-allyl-14β-ethylmarcfortine B;1-benzyl-14α-O-allyl-14β-ethylmarcfortine B;18a-ethyl-14α-O-allyl-14β-ethylmarcfortine B;18α-benzyl-14α-O-allyl-14β-ethylmarcfortine B;18α-methoxyethoxymethyl-14α-O-allyl-14β-ethylmarcfortine B; 1α-allyl-14α-O-allyl-14β-ethylmarcfortine B;18a-propargyl-14α-O-allyl-14β-ethylmarcfortine B; 1,18a-bis-ethyl-14α-O-allyl-14β-ethylmarcfortine B;1,18a-bis-benzyl-14α-O-allyl-14β-ethylmarcfortine B;18a-ethyl-24-methoxy-14α-O-allyl-14β-ethylmarcfortine B;1-palmitoyl-14α-O-allyl-14β-ethylmarcfortine A; 14α-hydroxy-14β-methyl-15α-methylmarcfortine A;1-acetoxymethyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;1-diethoxyphosphoryl-14α-hydroxy-14β-methyl-15α-methylxymarcfortine A;1-dimethylsulfamoyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;1-cyclopropylcarbonyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;2-bicyclo 2.2.1!heptanoyl-14α-hydroxy-14β-methyl-15α-methylmarcfortineA; 1-succinoyl-14αα-hydroxy-14β-methyl-15α-methylmarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-14β-methyl-15α-methylmarcfortineA; 1-(p-toluenesulfonyl)-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;1-acetyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;1-methyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;1-benzyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;1-dimethylcarbamoyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;1-methoxycarbonyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;14α-hydroxy-14β-methyl-15α-methylmarcfortine B;1-(p-toluenesulfonyl)-14α-hydroxy-14β-methyl-15α-methylmarcfortine B;1-ethyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine B;1-benzyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine B;18a-ethyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine B;18a-benzyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine B;18a-methoxyethoxymethyl-14-hydroxy-14β-methyl-15α-methylmarcfortine B;18a-allyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine B;18a-propargyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine B;1,18α-bis-ethyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine B; 1.18α-bis-benzyl-14α-hydroxy-14β-methyl-15α-methylmarcfortineB;18a-ethyl-24-methoxy-14-hydroxy-14β-methyl-15α-methylmarcfortine B;1-palmitoyl-14α-hydroxy-14β-methyl-15α-methylmarcfortine A;14α-hydroxy-15α-methylmarcfortine A;1-acetoxymethyl-14α-hydroxy-15α-methylmarcfortine A;1-diethoxyphosphoryl-14α-hydroxy-15α-methylxymarcfortine A;1-dimethylsulfamoyl-14α-hydroxy-15α-methylmarcfortine A;1-cyclopropylcarbonyl-14α-hydroxy-15α-methylmarcfortine A; 2-bicyclo2.2.1!heptanoyl-14α-hydroxy-15α-methylmarcfortine A;1-succinoyl-14α-hydroxy-15α-methylmarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-15α-methylmarcfortine A;1-(p-toluenesulfonyl)-14α-hydroxy-15c-methylmarcfortine A;1-acetyl-14α-hydroxy-15α-methylmarcfortine A;1-methyl-14α-hydroxy-15α-methylmarcfortine A;1-benzyl-14α-hydroxy-15α-methylmarcfortine A;1-dimethylcarbamoyl-14α-hydroxy-15α-methylmarcfortine A;1-methoxycarbonyl-14α-hydroxy-15α-methylmarcfortine A;14α-hydroxy-15α-methylmarcfortine B;1-(p-toluenesulfonyl)-14α-hydroxy-15α-methylmarcfortine B;1-ethyl-14α-hydroxy-15α-methylmarcfortine B;1-benzyl-14α-hydroxy-15α-methylmarcfortine B;18a-ethyl-14α-hydroxy-15α-methylmarcfortine B;18a-benzyl-14α-hydroxy-15α-methylmarcfortine B;18a-methoxyethoxymethyl-14α-hydroxy-15α-methylmarcfortine B;18a-allyl-14α-hydroxy-15α-methylmarcfortine B;18a-propargyl-14α-hydroxy-15α-methylmarcfortine B;1,18a-bis-ethyl-14α-hydroxy-15α-methylmarcfortine B;1,18a-bis-benzyl-14α-hydroxy-15α-methylmarcfortine B;18a-ethyl-24-methoxy-14α-hydroxy-15α-methylmarcfortine B;1-palmitoyl-14α-hydroxy-15α-methylmarcfortine A.
 9. A compound accordingto claim 1 selected from the group consistingof14α-hydroxy-14β-ethylmarcfortine A; 14α-hydroxy-14β-methylmarcfortineA; or 14α-hydroxy-14α-methyl-15α-methylmarcfortine A.
 10. A compoundaccording to claim 1, which is 14α-hydroxymarcfortine A.
 11. A compoundaccording to claim 1, which is 14α-hydroxy-15α-methylmarcfortine A. 12.A compound according to claim 1, which is14α-hydroxy-14β-methylmarcfortine A.
 13. A method for the treatment orprevention of helminth or arthropod infections in domesticated animalswhich comprises treating such animals with an effective amount of acompound of claim
 11. 14. A method for the treatment of insect ornematode pests of plants which comprises treating said plants or thesoil in which they grow with an effective amount of a compound ofclaim
 1. 15. A composition useful for the treatment and prevention ofhelminth or arthropod infections of domesticated animals which iscomprised of an inert carrier and a compound of claim
 1. 16. Acomposition useful for the prevention and treatment of insect ornematode pests of plants which is comprised of an inert carrier and acompound of claim
 1. 17. A compound selected from the group consisitingof:16-iodo-17-cyanomarcfortine A;1-acetoxymethyl-16-iodo-17-cyanomarcfortine A;1-diethoxyphosphoryl-16-iodo-17-cyanomarcfortine A;1-dimethylsulfamoyl-16-iodo-17-cyanomarcfortine A;1-cyclopropylcarbonyl-16-iodo-17-cyanomarcfortine A; 2-bicyclo2.2.1!heptanoyl-16-iodo-17-cyanomarcfortine A;1-succinoyl-16-iodo-17-cyanomarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-16-iodo-17-cyanomarcfortine A;1-(p-toluenesulfonyl)-16-iodo-17-cyanomarcfortine A;1-acetyl-16-iodo-17-cyanomarcfortine A;1-methyl-16-iodo-17-cyanomarcfortine A;1-benzyl-16-iodo-17-cyanomarcfortine A;1-dimethylcarbamoyl-16-iodo-17-cyanomarcfortine A;1-methoxycarbonyl-16-iodo-17-cyanomarcfortine A;16-iodo-17-cyanomarcfortine B;1-(p-toluenesulfonyl)-16-iodo-17-cyanomarcfortine B;1-ethyl-16-iodo-17-cyanomarcfortine B;1-benzyl-16-iodo-17-cyanomarcfortine B;18a-ethyl-16-iodo-17-cyanomarcfortine B;18a-benzyl-16-iodo-17-cyanomarcfortine B;18a-methoxyethoxymethyl-16-iodo-17-cyanomarcfortine B;18a-allyl-16-iodo-17-cyanomarcfortine B;18a-propargyl-16-iodo-17-cyanomarcfortine B;18a-ethyl-24-methoxy-24,25-dihydro-16-iodo-17-cyanomarcfortine B;1,18a-bis-ethyl-16-iodo-17-cyanomarcfortine B;1,18a-bis-benzyl-16-iodo-17-cyanomarcfortine B;18a-ethyl-24-methoxy-16-iodo-17-cyanomarcfortine B;1-palmitoyl-16-iodo-17-cyanomarcfortine A;16,17-dehydro-17-cyanomarcfortine A;1-acetoxymethyl-16,17-dehydro-17-cyanomarcfortine A;1-diethoxyphosphoryl-16,17-dehydro-17-cyanomarcfortine A;1-dimethylsulfamoyl-16,17-dehydro-17-cyanomarcfortine A;1-cyclopropylcarbonyl-16,17-dehydro-17-cyanomarcfortine A; 2-bicyclo2.2.1!heptanoyl-16,17-dehydro-17-cyanomarcfortine A;1-succinoyl-16,17-dehydro-17-cyanomarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-16,17-dehydro-17-cyanomarcfortine A;1-(p-toluenesulfonyl)-16,17-dehydro-17-cyanomarcfortine A;1-acetyl-16,17-dehydro-17-cyanomarcfortine A;1-methyl-16,17-dehydro-17-cyanomarcfortine A;1-benzyl-16,17-dehydro-17-cyanomarcfortine A;1-dimethylcarbamoyl-16,17-dehydro-17-cyanomarcfortine A;1-methoxycarbonyl-16,17-dehydro-17-cyanomarcfortine A;16,17-dehydro-17-cyanomarcfortine B;1-(p-toluenesulfonyl)-16,17-dehydro-17-cyanomarcfortine B;1-ethyl-16,17-dehydro-17-cyanomarcfortine B;1-benzyl-16,17-dehydro-17-cyanomarcfortine B;18a-ethyl-16,17-dehydro-17-cyanomarcfortine B;18a-benzyl-16,17-dehydro-17-cyanomarcfortine B;18a-methoxyethoxymethyl-16,17-dehydro-17-cyanomarcfortine B;18a-allyl-16,17-dehydro-17-cyanomarcfortine B;18a-propargyl-16,17-dehydro-17-cyanomarcfortine B;18a-ethyl-24-methoxy-24,25-dihydro-16,17-dehydro-17-cyanomarcfortine B;1,18a-bis-ethyl-16,17-dehydro-17-cyanomarcfortine B;1,18a-bis-benzyl-16,17-dehydro-17-cyanomarcfortine B;18a-ethyl-24-methoxy-16,17-dehydro-17-cyanomarcfortine B;1-palmitoyl-16,17-dehydro-17-cyanomarcfortine A; 17-ketomarcfortine A;1-acetoxymethyl-17-ketomarcfortine A;1-diethoxyphosphoryl-17-ketoxymarcfortine A;1-dimethylsulfamoyl-17-ketomarcfortine A;1-cyclopropylcarbonyl-17-ketomarcfortine A; 2-bicyclo2.2.1!heptanoyl-17-ketomarcfortine A; 1-succinoyl-17-ketomarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-17-ketomarcfortine A;1-(p-toluenesulfonyl)-17-ketomarcfortine A; 1-acetyl-17-ketomarofortineA; 1-methyl-17-ketomarcfortine A; 1-benzyl-17-ketomarcfortine A;1-dimethylcarbamoyl-17-ketomarcfortine A;1-methoxycarbonyl-17-ketomarcfortine A; 17-ketomarcfortine B;1-(p-toluenesulfonyl)-17-ketomarcfortine B; 1-ethyl-17-ketomarcfortineB; 1-benzyl-17-ketomarcfortine B; 18a-ethyl-17-ketomarcfortine B;18a-benzyl-17-ketomarcfortine B;18a-methoxyethoxymethyl-17-ketomarcfortine B;18a-allyl-17-ketomarcfortine B; 18a-propargyl-17-ketomarcfortine B;1,18a-bis-ethyl-17-ketomarcfortine B;1,18a-bis-benzyl-17-ketomarcfortine B;18a-ethyl-24-methoxy-17-ketomarcfortine B;1-palmitoyl-17-ketomarcfortine A; 15,16-dehydro-17-ketomarcfortine A;1-acetoxymethyl-15,16-dehydro-17-ketomarcfortine A;1-diethoxyphosphoryl-15,16-dehydro-17-ketoxymarcfortine A;1-dimethylsulfamoyl-15,16-dehydro-17-ketomarcfortine A;1-cyclopropylcarbonyl-15,16-dehydro-17-ketomarcfortine A; 2-bicyclo2.2.1!heptanoyl-15,16-dehydro-17-ketomarcfortine A;1-succinoyl-15,16-dehydro-17-ketomarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-15,16-dehydro-17-ketomarcfortine A;1-(p-toluenesulfonyl)-15,16-dehydro-17-ketomarcfortine A;1-acetyl-15,16-dehydro-17-ketomarcfortine A;1-methyl-15,16-dehydro-17-ketomarcfortine A;1-benzyl-15,16-dehydro-17-ketomarcfortine A;1-dimethylcarbamoyl-15,16-dehydro-17-ketomarcfortine A;1-methoxycarbonyl-15,16-dehydro-17-ketomarcfortine A;15,16-dehydro-17-ketomarcfortine B;1-(p-toluenesulfonyl)-15,16-dehydro-17-ketomarcfortine B;1-ethyl-15,16-dehydro-17-ketomarcfortine B;1-benzyl-15,16-dehydro-17-ketomarcfortine B;18a-ethyl-15,16-dehydro-17-ketomarcfortine B;18a-benzyl-15,16-dehydro-17-ketomarcfortine B;18a-methoxyethoxymethyl-15,16-dehydro-17-ketomarcfortine B;18a-allyl-15,16-dehydro-17-ketomarcfortine B;18a-propargyl-15,16-dehydro-17-ketomarcfortine B;1,18a-bis-ethyl-15,16-dehydro-17-ketomarcfortine B;1,18a-bis-benzyl-15,16-dehydro-17-ketomarcfortine B;18a-ethyl-24-methoxy-15,16-dehydro-17-ketomarcfortine B;1-palmitoyl-15,16-dehydro-17-ketomarcfortine A;14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;1-acetoxymethyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;1-diethoxyphosphoryl-14α-hydroxy-15,16-dehydro-17-ketoxymarcfortine A;1-dimethylsulfamoyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;1-cyclopropylcarbonyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;2-bicyclo 2.2.1!heptanoyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortineA; 1-succinoyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-15,16-dehydro-17-ketomarcfortineA; 1-(p-toluenesulfonyl)-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;1-acetyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;1-methyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;1-benzyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;1-dimethylcarbamoyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;1-methoxycarbonyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;1-(p-toluenesulfonyl)-14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;1-ethyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;1-benzyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;18a-ethyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;18a-benzyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;18a-methoxyethoxymethyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;18a-allyl-14αα-hydroxy-15,16-dehydro-17-ketomarcfortine B;18a-propargyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;1,18a-bis-ethyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;1,18a-bis-benzyl-14o-hydroxy-15,16-dehydro-17-ketomarcfortine B;18a-ethyl-24-methoxy-14α-hydroxy-15,16-dehydro-17-ketomarcfortine B;1-palmitoyl-14α-hydroxy-15,16-dehydro-17-ketomarcfortine A;14α-hydroxy-17-ketomarcfortine A;1-acetoxymethyl-14α-hydroxy-17-ketomarcfortine A;1-diethoxyphosphoryl-14α-hydroxy-17-ketoxymarcfortine A;1-dimethylsulfamoyl-14α-hydroxy-17-ketomarcfortine A;1-cyclopropylcarbonyl-14α-hydroxy-17-ketomarcfortine A; 2-bicyclo2.2.1!heptanoyl-14α-hydroxy-17-ketomarcfortine A;1-succinoyl-14α-hydroxy-17-ketomarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-17-ketomarcfortine A;1-(p-toluenesulfonyl)-14α-hydroxy-17-ketomarcfortine A;1-acetyl-14α-hydroxy-17-ketomarcfortine A;1-methyl-14α-hydroxy-17-ketomarcfortine A;1-benzyl-14α-hydroxy-17-ketomarcfortine A;1-dimethylcarbamoyl-14α-hydroxy-17-ketomarcfortine A;1-methoxycarbonyl-14α-hydroxy-17-ketomarcfortine A;14α-hydroxy-17-ketomarcfortine B;1-(p-toluenesulfonyl)-14α-hydroxy-17-ketomarcfortine B;1-ethyl-14α-hydroxy-17-ketomarcfortine B;1-benzyl-14α-hydroxy-17-ketomarcfortine B;18a-ethyl-14α-hydroxy-17-ketomarcfortine B;18a-benzyl-14α-hydroxy-17-ketomarcfortine B;18a-methoxyethoxymethyl-14α-hydroxy-17-ketomarcfortine B;18a-allyl-14α-hydroxy-17-ketomarcfortine B;18a-propargyl-14α-hydroxy-17-ketomarcfortine B; 1,18a-bis-ethyl-14α-hydroxy-17-ketomarcfortine B;1,18a-bis-benzyl-14α-hydroxy-17-ketomarcfortine B;18a-ethyl-24-methoxy-14α-hydroxy-17-ketomarcfortine B;1-palmitoyl-14α-hydroxy-17-ketomarcfortine A; 14,17-diketomarcfortine A;1-acetoxymethyl-14,17-diketomarcfortine A;1-diethoxyphosphoryl-14,17-diketoxymarcfortine A;1-dimethylsulfamoyl-14,17-diketomarcfortine A;1-cyclopropylcarbonyl-14,17-diketomarcfortine A; 2-bicyclo2.2.1!heptanoyl-14,17-diketomarcfortine A;1-succinoyl-14,17-diketomarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-14,17-diketomarcfortine A;1-(p-toluenesulfonyl)-14,17-diketomarcfortine A;1-acetyl-14,17-diketomarcfortine A; 1-methyl-14,17-diketomarcfortine A;1-benzyl-14,17-diketomarcfortine A;1-dimethylcarbamoyl-14,17-diketomarcfortine A;1-methoxycarbonyl-14,17-diketomarcfortine A; 14,17-diketomarcfortine B;1-(p-toluenesulfonyl)-14,17-diketomarcfortine B;1-ethyl-14,17-diketomarcfortine B; 1-benzyl-14,17-diketomarcfortine B;1α -ethyl-14,17-diketomarcfortine B; 18a-benzyl-14,17-diketomarcfortineB; 18a-methoxyethoxymethyl-14,17-diketomarcfortine B;18a-allyl-14,17-diketomarcfortine B;18a-propargyl-14,17-diketomarcfortine B;1,18a-bis-ethyl-14,17-diketomarcfortine B;1,18a-bis-benzyl-14,17-diketomarcfortine B;18a-ethyl-24-methoxy-14,17-diketomarcfortine B;1-palmitoyl-14,17-diketomarcfortine A;15,16-dehydro-14,17-diketomarcfortine A;1-acetoxymethyl-15,16-dehydro-14,17-diketomarcfortine A;1-diethoxyphosphoryl-15,16-dehydro-14,17-diketoxymarcfortine A;1-dimethylsulfamoyl-15,16-dehydro-14,17-diketomarcfortine A;1-cyclopropylcarbonyl-15,16-dehydro-14,17-diketomarcfortine A; 2-bicyclo2.2.1!heptanoyl-15,16-dehydro-14,17-diketomarcfortine A;1-succinoyl-15,16-dehydro-14,17-diketomarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-15,16-dehydro-14,17-diketomarcfortine A;1-(p-toluenesulfonyl)-15,16-dehydro-14,17-diketomarcfortine A;1-acetyl-15,16-dehydro-14,17-diketomarcfortine A;1-methyl-15,16-dehydro-14,17-diketomarcfortine A;1-benzyl-15,16-dehydro-14,17-diketomarcfortine A;1-dimethylcarbamoyl-15,16-dehydro-14,17-diketomarcfortine A;1-methoxycarbonyl-15,16-dehydro-14,17-diketomarcfortine A;15,16-dehydro-14,17-diketomarcfortine B;1-(p-toluenesulfonyl)-15,16-dehydro-14,17-diketomarcfortine B;1-ethyl-15,16-dehydro-14,17-diketomarcfortine B;1-benzyl-15,16-dehydro-14, 17-diketomarcfortine B;18a-ethyl-15,16-dehydro-14,17-diketomarcfortine B;18a-benzyl-15,16-dehydro-14,17-diketomarcfortine B;18a-methoxyethoxymethyl-15,16-dehydro-14,17-diketomarcfortine B;18a-allyl-15,16-dehydro-14,17-diketomarcfortine B;18a-propargyl-15,16-dehydro-14,17-diketomarcfortine B;1,18a-bis-ethyl-15,16-dehydro-14,17-diketomarcfortine B;1,18a-bis-benzyl-15,16-dehydro-14,17-diketomarcfortine B;18a-ethyl-24-methoxy-15,16-dehydro-14,17-diketomarcfortine B;1-palmitoyl-15,16-dehydro-14,17-diketomarcfortine A;14α-hydroxy-14α-methyl-17-ketomarcfortine A;1-acetoxymethyl-14α-hydroxy-14β-methyl-17-ketomarcfortine A;1-diethoxyphosphoryl-14α-hydroxy-14β-methyl-17-ketoxymarcfortine A;1-dimethylsulfamoyl-14α-hydroxy-14β-methyl-17-ketomarcfortine A;1-cyclopropylcarbonyl-14α-hydroxy-14β-methyl-17-ketomarcfortine A;2-bicyclo 2.2. 1!heptanoyl-14α-hydroxy-14β-methyl-17-ketomarcfortine A;1-succinoyl-14α-hydroxy-14β-methyl-17-ketomarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-141-methyl-17-ketomarcfortineA; 1-(p-toluenesulfonyl)-14α-hydroxy-14β-methyl-17-ketomarcfortine A;1-acetyl-14α-hydroxy-14β-methyl-17-ketomarcfortine A;1-methyl-14α-hydroxy-14β-methyl-17-ketomarcfortine A;1-benzyl-14α-hydroxy-14β-methyl-17-ketomarcfortine A;1-dimethylcarbamoyl-14α-hydroxy-14β-methyl-17-ketomarcfortine A;1-methoxycarbonyl-14α-hydroxy-14β-methyl-17-ketomarcfortine A;14α-hydroxy-14β-methyl-17-ketomarcfortine B;1-(p-toluenesulfonyl)-14α-hydroxy-14β-methyl-17-ketomarofortine B;1-ethyl-14α-hydroxy-14β-methyl-17-ketomarcfortine B;1-benzyl-14α-hydroxy-14β-methyl-17-ketomarcfortine B;18a-ethyl-14α-hydroxy-14β-methyl-17-ketomarcfortine B;18a-benzyl-14α-hydroxy-14β-methyl-17-ketomarcfortine B;18a-methoxyethoxymethyl-14α-hydroxy-14β-methyl-17-ketomarcfortine B;18a-allyl-14x-hydroxy-14β-methyl-17-ketomarcfortine B;18a-propargyl-14α-hydroxy-14β-methyl-17-ketomarcfortine B;1,18a-bis-ethyl-14α-hydroxy-14β-methyl-17-ketomarcfortine B; 1.18α-bis-benzyl-14α-hydroxy-14β-methyl-17-ketomarcfortineB;18α-ethyl-24-methoxy-14α-hydroxy-14β-methyl-17-ketomarcfortine B;1-palmitoyl-14α-hydroxy-14β-methyl-17-ketomarcfortine A;14-ketomarcfortine A; 1-acetoxymethyl-14-ketomarcfortine A;1-diethoxyphosphoryl-14-ketoxymarcfortine A;1-dimethylsulfamoyl-14-ketomarcfortine A;1-cyclopropylcarbonyl-14-ketomarcfortine A; 2-bicyclo2.2.1!heptanoyl-14-ketomarcfortine A; 1-succinoyl-14-ketomarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-14-ketomarcfortine A;1-(p-toluenesulfonyl)-14-ketomarcfortine A; 1-acetyl-14-ketomarcfortineA; 1-methyl-14-ketomarcfortine A; 1-benzyl-14-ketomarcfortine A;1-dimethylcarbamoyl-14-ketomarcfortine A;1-methoxycarbonyl-14-ketomarcfortine A; 14-ketomarcfortine B;1-(p-toluenesulfonyl)-14-ketomarcfortine B; 1-ethyl-14-ketomarcfortineB; 1-benzyl-14-ketomarcfortine B; 18a-ethyl-14-ketomarcfortine B;18a-benzyl-14-ketomarcfortine B;18a-methoxyethoxymethyl-14-ketomarcfortine B;18a-allyl-14-ketomarcfortine B; 18a-propargyl-14-ketomarcfortine B;1,18a-bis-ethyl-14-ketomarcfortine B;1,18a-bis-benzyl-14-ketomarcfortine B;18a-ethyl-24-methoxy-14-ketomarcfortine B;1-palmitoyl-14-ketomarcfortine A; 16-dithio-17-ketomarcfortine A;1-acetoxymethyl-16-dithio-17-ketomarcfortine A;1-diethoxyphosphoryl-16-dithio-17-ketoxymarcfortine A;1-dimethylsulfamoyl-16-dithio-17-ketomarcfortine A;1-cyclopropylcarbonyl-16-dithio-17-ketomarcfortine A; 2-bicyclo2.2.1!heptanoyl-16-dithio-17-ketomarcfortine A;1-succinoyl-16-dithio-17-ketomarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-16-dithio-17-ketomarofortine A;1-(p-toluenesulfonyl)-16-dithio-17-ketomarcfortine A;1-acetyl-16-dithio-17-ketomarcfortine A;1-methyl-16-dithio-17-ketomarcfortine A;1-benzyl-16-dithio-17-ketomarcfortine A;1-dimethylcarbamoyl-16-dithio-17-ketomarcfortine A;1-methoxycarbonyl-16-dithio-17-ketomarcfortine A;16-dithio-17-ketomarcfortine B;1-(p-toluenesulfonyl)-16-dithio-17-ketomarcfortine B;1-ethyl-16-dithio-17-ketomarcfortine B;1-benzyl-16-dithio-17-ketomarcfortine B;18a-ethyl-16-dithio-17-ketomarcfortine B;18a-benzyl-16-dithio-17-ketomarcfortine B;18a-methoxyethoxymethyl-16-dithio-17-ketomarcfortine B;18a-allyl-16-dithio-17-ketomarcfortine B;18a-propargyl-16-dithio-17-ketomarcfortine B;1,18a-bis-ethyl-16-dithio-17-ketomarcfortine B;1,18a-bis-benzyl-16-dithio-17-ketomarcfortine B;18a-ethyl-24-methoxy-16-dithio-17-ketomarcfortine B;1-palmitoyl-16-dithio-17-ketomarcfortine A;16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;1-acetoxymethyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;1-diethoxyphosphoryl-16-thiophenyl-15,16-dehydro-17-ketoxymarcfortine A;1-dimethylsulfamoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;1-cyclopropylcarbonyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;2-bicyclo 2.2.1!heptanoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortineA; 1-succinoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortineA; 1-(p-toluenesulfonyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortineA; 1-acetyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;1-methyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;1-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;1-dimethylcarbamoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;1-methoxycarbonyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;1-(p-toluenesulfonyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;1-ethyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;1-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;18a-ethyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;18a-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;18a-methoxyethoxymethyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortineB; 18a-allyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;18a-propargyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;1,18a-bis-ethyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;1,18a-bis-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;18a-ethyl-24-methoxy-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;1-palmitoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;1-acetoxymethyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;1-diethoxyphosphoryl-16-thiophenyl-15,16-dehydro-17-ketoxymarcfortine A;1-dimethylsulfamoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;1-cyclopropylcarbonyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;2-bicyclo 2.2.1!heptanoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortineA; 1-succinoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortineA; 1-(p-toluenesulfonyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortineA; 1-acetyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;1-methyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;1-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;1-dimethylcarbamoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;1-methoxycarbonyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;1-(p-toluenesulfonyl)-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;1-ethyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;1-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;18a-ethyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;18a-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;18a-methoxyethoxymethyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortineB; 18a-allyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;18a-propargyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;1,18a-bis-ethyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;1,18a-bis-benzyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;18a-ethyl-24-methoxy-16-thiophenyl-15,16-dehydro-17-ketomarcfortine B;1-palmitoyl-16-thiophenyl-15,16-dehydro-17-ketomarcfortine A;14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine A;1-acetoxymethyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine A;1-diethoxyphosphoryl-14α-hydroxy-14β-methyl-15α-methyl-17-ketoxymarcfortineA;1-dimethylsulfamoyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineA;1-cyclopropylcarbonyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineA; 2-bicyclo2.2.1!heptanoyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine A;1-succinoyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineA;1-(p-toluenesulfonyl)-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineA; 1-acetyl-14α-hydroxy-141-methyl-15α-methyl-17-ketomarcfortine A;1-methyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine A;1-benzyl-14α-hydroxy-141-methyl-15α-methyl-17-ketomarcfortine A;1-dimethylcarbamoyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineA;1-methoxycarbonyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineA; 14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine B;1-(p-toluenesulfonyl)-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineB; 1-ethyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine B;1-benzyl-14α-hydroxy-141-methyl-15α-methyl-17-ketomarcfortine B;18a-ethyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine B;18a-benzyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine B;18a-methoxyethoxymethyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineB; 18a-allyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine B;18a-propargyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine B;1,18a-bis-ethyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine B;1,18a-bis-benzyl-14α-hydroxy-14β-methyl- 15α-methyl-17-ketomarcfortineB;18a-ethyl-24-methoxy-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortineB; 1-palmitoyl-14α-hydroxy-14β-methyl-15α-methyl-17-ketomarcfortine A;14α-hydroxy-15α-methyl-17-ketomarcfortine A;1-acetoxymethyl-14α-hydroxy-15α-methyl-17-ketomarcfortine A;1-diethoxyphosphoryl-14α-hydroxy-15α-methyl-17-ketoxymarcfortine A;1-dimethylsulfamoyl-14α-hydroxy-15α-methyl-17-ketomarcfortine A;1-cyclopropylcarbonyl-14α-hydroxy-15α-methyl-17-ketomarcfortine A;2-bicyclo 2.2.1!heptanoyl-14α-hydroxy-15α-methyl-17-ketomarcfortine A;1-succinoyl-14α-hydroxy-15α-methyl-17-ketomarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-14α-hydroxy-15α-methyl-17-ketomarcfortineA; 1-(p-toluenesulfonyl)-14α-hydroxy-15α-methyl-17-ketomarcfortine A;1-acetyl-14α-hydroxy-15α-methyl-17-ketomarcfortine A;1-methyl-14α-hydroxy-15α-methyl-17-ketomarcfortine A;1-benzyl-14α-hydroxy-15α-methyl-17-ketomarcfortine A;1-dimethylcarbamoyl-14α-hydroxy-15α-methyl-17-ketomarcfortine A;1-methoxycarbonyl-14α-hydroxy-15α-methyl-17-ketomarcfortine A;14α-hydroxy-15α-methyl-17-ketomarcfortine B;1-(p-toluenesulfonyl)-14α-hydroxy-15α-methyl-17-ketomarcfortine B;1-ethyl-14α-hydroxy-15α-methyl-17-ketomarcfortine B;1-benzyl-14α-hydroxy-15α-methyl-17-ketomarcfortine B;18a-ethyl-14α-hydroxy-15α-methyl-17-ketomarcfortine B;18a-benzyl-14α-hydroxy-15α-methyl-17-ketomarcfortine B;18a-methoxyethoxymethyl-14α-hydroxy-15α-methyl-17-ketomarcfortine B;18a-allyl-14α-hydroxy-15α-methyl-17-ketomarcfortine B;18a-propargyl-14α-hydroxy-15α-methyl-17-ketomarcfortine B;1,18a-bis-ethyl-14α-hydroxy-15α-methyl-17-ketomarcfortine B;1,18a-bis-benzyl-14α-hydroxy-15α-methyl-17-ketomarcfortine B;18a-ethyl-24-methoxy-14α-hydroxy-15α-methyl-17-ketomarcfortine B;1-palmitoyl-14α-hydroxy-15α-methyl-17-ketomarcfortine A;15α-methyl-14,17-diketomarcfortine A;1-acetoxymethyl-15α-methyl-14,17-diketomarcfortine A;1-diethoxyphosphoryl-15α-methyl-14,17-diketoxymarcfortine A;1-dimethylsulfamoyl-15α-methyl-14,17-diketomarcfortine A;1-cyclopropylcarbonyl-15α-methyl-14,17-diketomarcfortine A; 2-bicyclo2.2.1 !heptanoyl-15α-methyl-14,17-diketomarcfortine A;1-succinoyl-15α-methyl-14,17-diketomarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-15α-methyl-14,17-diketomarcfortine A;1-(p-toluenesulfonyl)-15α-methyl-14,17-diketomarcfortine A;1-acetyl-15α-methyl-14,17-diketomarcfortine A;1-methyl-15α-methyl-14,17-diketomarcfortine A;1-benzyl-15α-methyl-14,17-diketomarcfortine A;1-dimethylcarbamoyl-15α-methyl-14,17-diketomarcfortine A;1-methoxycarbonyl-15-methyl-14,17-diketomarcfortine A;15α-methyl-14,17-diketomarcfortine B;1-(p-toluenesulfonyl)-15α-methyl-14,17-diketomarcfortine B;1-ethyl-15α-methyl-14,17-diketomarcfortine B;1-benzyl-15α-methyl-14,17-diketomarcfortine B;18a-ethyl-15α-methyl-14,17-diketomarcfortine B;18a-benzyl-15α-methyl-14,17-diketomarcfortine B;18a-methoxyethoxymethyl-15αα-methyl-14,17-diketomarcfortine B;18a-allyl-15α-methyl-14,17-diketomarcfortine B;18a-propargyl-15α-methyl-14,17-diketomarcfortine B;1,18a-bis-ethyl-15α-methyl-14,17-diketomarcfortine B;1,18a-bis-benzyl-15α-methyl-14, 17-diketomarcfortine B;18a-ethyl-24-methoxy-15α-methyl-14,17-diketomarcfortine B;1-palmitoyl-15α-methyl-14, 17-diketomarcfortine A;1-palmitoyl-15α-methyl-14,17-diketomarcfortine D;14,15-dehydro-16,17-diketomarcfortine A;1-acetoxymethyl-14,15-dehydro-16,17-diketomarcfortine A;1-diethoxyphosphoryl-14,15-dehydro-16,17-diketoxymarcfortine A;1-dimethylsulfamoyl-14,15-dehydro-16,17-diketomarcfortine A;1-cyclopropylcarbonyl-14,15-dehydro-16,17-diketomarcfortine A; 2-bicyclo2.2. 1!heptanoyl-14,15-dehydro-16,17-diketomarcfortine A;1-succinoyl-14,15-dehydro-16,17-diketomarcfortine A;1-(2,4-dinitrobenzenesulfenyl)-14,15-dehydro-16,17-diketomarcfortine A;24-propoxy-24,25-dihydro-14,15-dehydro-16,17-diketomarcfortine A;1-(p-toluenesulfonyl)-14,15-dehydro-16,17-diketomarcfortine A;1-acetyl-14,15-dehydro-16,17-diketomarcfortine A;1-methyl-14,15-dehydro-16,17-diketomarcfortine A;1-benzyl-14,15-dehydro-16,17-diketomarcfortine A;1-dimethylcarbamoyl-14,15-dehydro-16,17-diketomarcfortine A;1-methoxycarbonyl-14,15-dehydro-16,17-diketomarcfortine A;14,15-dehydro-16,17-diketomarcfortine B; 1-(p-toluenesulfonyl)-14,15-dehydro-16,17-diketomarcfortine B;1-ethyl-14,15-dehydro-16,17-diketomarcfortine B;1-benzyl-14,15-dehydro-16,17-diketomarcfortine B;18a-ethyl-14,15-dehydro-16,17-diketomarcfortine B;18a-benzyl-14,15-dehydro-16,17-diketomarcfortine B;18a-methoxyethoxymethyl-14,15-dehydro-16,17-diketomarcfortine B;18a-allyl-14,15-dehydro-16,17-diketomarcfortine B;18a-propargyl-14,15-dehydro-16,17-diketomarcfortine B;1,18a-bis-ethyl-14,15-dehydro-16,17-diketomarcfortine B;1,18a-bis-benzyl-14,15-dehydro-16,17-diketomarcfortine B;18a-ethyl-24-methoxy-14,15-dehydro-16,17-diketomarcfortine B;1-palmitoyl-14,15-dehydro-16,17-diketomarcfortine A.